Articles comprising a polyimide solvent cast film having a low coefficient of thermal expansion and method of manufacture thereof

ABSTRACT

An article comprises a solvent cast film comprising a polyetherimide comprising structural units derived from a dianhydride component selected from the group consisting of 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4′-oxydiphthalic anhydride, and combinations thereof, and a diamine component. The polyetherimide has a glass transition temperature that is at least 190° C. The film has a coefficient of thermal expansion of less than 60 ppm/° C., a thickness from 0.1 to 250 micrometers, and less than 5% residual solvent by weight. The film has less than 15 molar % of a member selected from the group consisting of biphenyltetracarboxylic acid, dianhydrides of biphenyltetracarboxylic acid, esters of biphenyltetracarboxylic acid, and combinations thereof.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Application Ser. No. 60/805,821, filed Jun. 26, 2006, which is incorporated herein by reference in its entirety.

FIELD

The present invention is directed to articles comprising a solvent cast film comprising a polyimide and methods for the manufacture of such articles. The film is formed by polymerization of a dianhydride component and a diamine component, and has a Tg of between 180° C. and 450° C., specifically 190° C. or greater, and wherein the film has: a) a CTE of less than 70 ppm/° C., specifically less than 60 ppm/° C.; b) a thickness between 0.1 micrometers and 250 micrometers, specifically 5 to 250 micrometers; and, c) contains less than 5% residual solvent by weight.

BACKGROUND OF THE INVENTION

Thermoplastic sheets and films have a broad range of applications. For instance, thermoplastic films and sheets can be found in automotive applications, electronic applications, military applications, appliances, industrial equipment, and furniture.

Thermoplastic sheets and film can be reinforced or non-reinforced, porous or nonporous and can comprise a single thermoplastic or multiple thermoplastics. When a thermoplastic sheet or film comprises multiple thermoplastics it may be as a blend, as layers, or both.

One important use of films is their use as substrates, or coatings on, flexible circuit applications. In order to serve in this role a new film should meet two requirements critical for flexible circuit substrates, namely low coefficient of thermal expansion (CTE) and high temperature survivability (especially when a high temperature fabrication step is employed).

Low CTE is necessary to match, as closely as possible, the CTE of copper (CTE=17 ppm/° C.). This keeps the film from curling upon temperature change when the film is a substrate for a copper layer, or copper circuit traces. Low CTE also prevents unmatched changes in dimension between the copper and substrate layers upon thermal cycling, which increases the lifetime of the final flexible circuit by reducing stress and fatigue on the patterned copper traces. In other words, the properties of flexible circuit boards are benefited when their film substrate and applied conductive metal layer expand and contract at the same rate. When these layers don't expand and contract at the same rate issues regarding the adherence, and orientation of the layers can and do arise. While a CTE of less than 70 ppm/° C., specifically less than 60 ppm/° C., even more specifically less than 30 ppm/° C. will allow low warpage upon thermal cycling and is a common goal, better results will be achieved as the CTE of the film becomes closer to the CTE of copper.

CTE is tested by a TMA or Thermomechanical Analysis. The dimension change of a film sample is determined as a function of temperature, and from the slope of this change, the CTE is calculated. Typically, the CTE must be measured for the temperature range that the film is expected to see during flex circuit processing. A temperature range of 20 to 250° C. is a reasonable temperature range for determination of the CTE.

High temperature survivability can also be an important property for the substrate film to survive the soldering process during flex circuit fabrication. The film should exhibit survivability for short periods at elevated temperatures of, for example, 260° C. for new lead-free soldering processes. The standard test for temperature survivability is the solder float test, where a small piece of film is affixed to a cork and is immersed for 10 seconds in molten solder. The film is then removed, the solder is wiped off, and the film is examined. If there is any visible warpage or bubbling, the film fails the test. While there is not a standard thickness for this test, the minimum thickness at which the film passes the solder float test can be reported. Temperatures of 260° C. and 288° C. are standard solder float temperatures for lead-eutectic and lead-free solders, respectively.

Low CTE and high temperature resistance requirements for flexible circuit substrates have been addressed through the use of polyimide films. Many commercial polyimide (PI) films have a high glass transition temperature (greater than 350° C.), and can be partially crosslinked, giving exceptional temperature survivability. The polymer molecules in these films are stressed slightly as they are produced, leading to alignment of the polymer molecules and giving PI films a low CTE. Since the films never see temperatures above the glass transition temperature (Tg) of the material, the stress is never able to relax and the films are dimensionally stable at flex fabrication temperatures.

As thermoplastic sheets and films are used in an increasing wide array of applications the need for thermoplastic sheets and films that can withstand elevated temperatures for appropriate periods of time without substantial degradation is growing. There is a continuing need for films having: a) a CTE under seventy ppm/° C., specifically under thirty ppm/° C. and as close to the CTE of copper as technically possible; and b) high thermal survivability.

SUMMARY OF THE INVENTION

The present disclosure is directed to articles comprising thermoplastic sheets and films that have a broad range of applications. For instance, thermoplastic films and sheets can be found in automotive applications, electronic applications, military applications, appliances, industrial equipment, and furniture.

In one embodiment, an article comprises a solvent cast film comprising a polyimide comprising structural units derived from polymerization of a dianhydride component comprising a dianhydride selected from the group consisting of 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4′-oxydiphthalic anhydride, and combinations thereof, and a diamine component, wherein the polyimide has a glass transition temperature of 190° C. or greater; wherein the film has a coefficient of thermal expansion of less than 60 ppm/° C., a thickness from 0.1 to 250 micrometers, and less than 5% residual solvent by weight; wherein the polyimide has less than 15 molar % of structural units derived from a member of the group consisting of biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, an ester of biphenyltetracarboxylic acid, and combinations thereof.

An article comprising a solvent cast polyetherimide film comprises: a polyetherimide comprising structural units derived from the polymerization of a dianhydride component comprising a dianhydride selected from the group consisting of 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4′-oxydiphthalic anhydride, and combinations thereof, with a diamine component comprising a diamine selected from the group consisting of 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, p-phenylenediamine, and combinations thereof; wherein the polyetherimide comprises less than 15 mole % of structural units selected derived from the group consisting of biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, an ester of biphenyltetracarboxylic acid, and combinations thereof; wherein the polyetherimide has a glass transition temperature from 190° C. to 400° C., and wherein the film has a coefficient of thermal expansion of less than 60 ppm/° C., a thickness from 0.1 to 250 micrometers, and less than 5% residual solvent by weight; wherein the film has a coefficient of thermal expansion that is within +20 ppm/° C. of the coefficient of thermal expansion of copper, silicon, aluminum, gold, silver, nickel, a glass, a ceramic, or a polymer; and wherein the solvent is selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidinone, dimethylsulfoxide, sulfolane, tetrahydrofuran, benzophenone, cyclohexanone, phenol, o-cresol, p-cresol, m-cresol, phenol, ethylphenol, isopropylphenol, t-butylphenol, xylenol, mesitol, chlorophenol, dichlorophenol, phenylphenol, a monoalkyl ether of ethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoalkyl ether of diethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoaryl ether glycol, a monoaryl ether of propylene glycol, tetramethylurea, phenoxy ethanol, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, N-cyclohexylpyrrolidinone, ethyl lactate, an ionic liquid, and combinations thereof.

A method of manufacture of the above-described article comprises forming the solvent cast polyimide film on a substrate.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graph of the time/temperature imidization profile used to prepare polyetherimides as described herein.

DETAILED DESCRIPTION OF THE INVENTION

As thermoplastic sheets and films are used in the specification and the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings. The singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art. Compounds are described using standard nomenclature.

Other than in the operating examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as modified in all instances by the term “about.” The term “combination thereof” means that one or more of the listed components is present, optionally together with one or more like components not listed. Various numerical ranges are disclosed in this patent application. Because these ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations. The endpoints of all ranges directed to the same component or property are inclusive of the endpoint and independently combinable.

For purposes of the present invention, a “film” is a flat section of thermoplastic resin or other material that is extremely thin in comparison to its length and breadth.

The term “casting” refers to a process of molding or forming wherein impressions are made with fluent or molten materials as by pouring into a mold or onto a sheet with hardening or setting of said material in said mold or on said sheet.

A “solvent cast film” is a film formed through the casting of fluids on a forming surface to form a sheet or web with removal of solvent from the cast liquid.

All ASTM tests and data are from the 1991 edition of the Annual Book of ASTM Standards unless otherwise indicated.

“Coefficient of thermal expansion” is the increment in volume of a unit volume of polymer for a rise of temperature of 1° C. at constant pressure. For the present invention CTE measurements were performed by thermo-mechanical analysis (TMA) with a thermal ramp rate of 5° C./minute. Test specimen dimensions were 23 mm in length by 5 mm in width. Test specimens were subjected to a first heat from 0° C. to 250° C. at 5° C./min heating rate and CTE values were determined under a force of 0.05 Newtons from the slope of length change over the temperature range from 30° C. to 200° C.

“Chemical resistance” is the ability of solid materials to resist damage by chemical reactivity or solvent action, and can be determined in accordance with ASTM Test D543-06

“Dielectric Constant” (permittivity constant): between any two electrically charged bodies there is a force (attraction or repulsion) that varied according to the strength of the charges, q1 and q2, the distance between the bodies, r, and a characteristic of the medium separating the bodies (the dielectric) known as the dielectric constant, ∈. This force is given by the equation: F=q1·q2/(∈·r²).

“Flexural Modulus” (flex modulus) is the ratio, within the elastic limit, of the applied stress in the outermost fibers of a test specimen in three-point, static flexure, to the calculated strain in those outermost fibers, and can be determined according to ASTM Test D790 or D790M.

“Flexural Strength” (flexural modulus of rupture) is the maximum calculated stress in the outermost fibers of a test bar subjected to three-point loading at the moment of cracking or breaking. ASTM Test D 790 and D 790M are widely used for measuring this property. For most plastics, flexural strength is usually substantially higher than the straight tensile strength.

“Glass Transition” is a reversible change that occurs in an amorphous polymer or in amorphous regions of a partly crystalline polymer when it is heated from a very low temperature into a certain range, peculiar to each polymer, characterized by a rather sudden change from a hard, glassy, or brittle condition to a flexible or elastomeric condition. Physical properties such as coefficient of thermal expansion, specific heat, and density, usually undergo changes in their temperature derivatives at the same time. During the transition, the molecular chains, normally coiled, tangled, and motionless at the lower temperatures, become free to rotate and slip past each other.

“Glass Transition Temperature” (Tg) is the approximate midpoint of the temperature range over which the glass transition occurs. Tg is not obvious (like a melting point), and is detected by changes, with rising temperature, in secondary properties such as the rate of change with temperature of specific volume or electrical or mechanical properties. Moreover, the observed Tg can vary significantly with the specific property chosen for observation and on experimental details such as the rate of heating or electrical frequency. A reported Tg should therefore be viewed as an estimate. The most reliable estimates are normally obtained from the loss peak in dynamic-mechanical tests or from dilatometric data. For purposes of the present invention, the glass transition temperature (Tg) is determined by the maximum point of the tan delta curve. Tg can also be determined by the inflection of the DSC (Differential Scanning Calorimetry) trace (ASTM Test D3148).

“Melting Temperature” (hereafter identified by its symbol “T_(m)”) is the temperature at which the thermal energy in a solid material is sufficient to overcome the intermolecular forces of attraction in the crystalline lattice so that the lattice breaks down and the material becomes a liquid, i.e. it melts. According to the present invention the T_(m) is measured according to ASTM test D3148.

“Melt Viscosity” is the resistance to shear in a molten resin, quantified as the quotient of shear stress divided by shear rate at any point in the flowing material. Elongational viscosity, which comes into play in the drawing of extrudates, is analogously defined. In polymers, the viscosity depends not only on temperature and, less strongly, on pressure, but also on the level of shear stress (or shear rate). For purposes of the present invention melt viscosity is determined at 380° C. as measured by capillary rheology according to ASTM D3835.

“Moisture Absorption” is the pickup of water vapor by a material upon exposure for a definite time interval in an atmosphere of specified humidity and temperature. No ASTM test exists for this property. Moisture absorption at 50% relative humidity and by immersion in water is measured by weight gain.

“Tensile Modulus” or “Modulus of Elasticity” is the ratio of nominal tensile stress to the corresponding elongation below the proportional limit of the material. The relevant ASTM test is D638.

“Tensile Strength” is the maximum nominal stress sustained by a test specimen being pulled from both ends, at a specified temperature and at a specified rate of stretching. When the maximum nominal stress occurs at the Yield Point it shall be designated tensile strength at yield. When it occurs at break, it shall be designated tensile strength at break. The ASTM test for plastics is D638 (metric, D638M). The SI unit of tensile strength is the pascal (N/m²).

Gallery spacing or d-spacing is the distance between the various microplates that make up a nanosilicate (synonymous with nano-clay, nano clay, or nanoclay). The changes in the gallery spacing appear to be dependent on the composition of the modified nanosilicate and the solvent.

“Intercalate” refers to a process by which the d-spacing is increased by the incorporation of a modifier, solvent, or a polymer between the plates. A modified nano clay has a d-spacing that is greater than that for the same unmodified nano clay.

“Exfoliate” refers to the complete separation of the plates that make up the clay structure. Sometimes there is incomplete exfoliation to smaller structures that have multiple plate that are called tactoids.

“Polyamic acid solution” (also known as poly-amide-acid, poly(amic acid), amic acid, polyamicacid, poly(amic acid), poly(amide acid), poly(amic) acid, poly(amide-acid), or polyamic-acid) is a solution containing amic acid units that have the capability of reacting with surrounding organic moieties to form imide groups.

“Polyimide” as used herein refers to polymers comprising repeating imide functional groups, and optionally additional functional groups such as amides and/or ethers. “Polyimide” accordingly includes within its scope polyamide imides and polyetherimides.

The term “inerted” means that the atmosphere in a container is replaced with an inert gas, such as for example, nitrogen.

“Recycle” means that all or a part of the polymer according to the present invention can be re-used for the original utility for which the polymer was made. For example, if the original use of the polymer as a solvent cast film for a flexible circuit board, all or part of the polymer can be recycled and be re-dissolved in solvent with or without the use of additional monomer or polymer. Recycle can also mean that the polymer can be re-used either in part or completely by another reprocessing method into another utility such as an injected molded part.

When structural units of chemical moieties are said to be formally derived from a precursor moiety herein, there is no implied limitation on the actual chemical reaction which may be used to produce the chemical moiety. For example when a chemical moiety such as a polyetherimide is said to have structural units formally derived from a dianhydride and a diamine, then any known method could be used to prepare the polyetherimide, including reaction of a dianhydride and a diamine, or a displacement reaction between a phenoxide species and an imide bearing a displaceable group, or other known method, it only being necessary that the chemical moiety comprise structural units which may be represented in the stated precursor moiety.

The present disclosure is directed to articles comprising solvent cast films comprising a dianhydride component and a diamine component and a Tg of between 180° C. and 450° C., specifically 190° C. or greater, and wherein the film has: a) a CTE of less than 70 ppm/° C., specifically less than 60 ppm/° C.; b) a thickness of between 5 micrometers and 250 micrometers, specifically 0.1 to 250 micrometers; and, c) contains less than 5% residual solvent by weight.

The solvent cast film according to the present invention can be made of at least one polyimide have a Tg of between 180° C. and 450° C. In another embodiment, the polyimide has a Tg of 190° C. or greater, specifically 190° C. to 500° C., more specifically 190° C. to 400° C. The skilled artisan will appreciate that the Tg of any particular polyimide can vary widely depending upon factors including the choice of dianhydride monomer, the number of different dianhydride monomers (structures as opposed to units), the choice of diamine monomer, the number of different diamine monomers (structures as opposed to units), processing conditions during production of the film, type of imidization process used to cure the polymer, etc. The skilled artisan will appreciate the ability to create a polymer having a desired Tg anywhere within the aforementioned range of Tg's, depending on the monomers used, the use of endcapping, etc.

The type of polyimide making up the film is similarly variable. The present invention specifically includes random and block polymers and co-polymers in all combinations of the one or more dianhydride and the one or more diamine from which the present polyimides can be made. More than one type of polyimide can be present, for example a combination of a polyamideimide and a polyetherimide, or two different kinds of polyetherimide. Also, the present invention is directed to solvent cast films comprising one or more polyimide films that includes other polymers selected from the group consisting of amorphous thermoplastic polymers including PPSU (polyphenylene sulfone), PSU (polysulfone), PC (polycarbonate), PPO (polyphenylene ether), PMMA (polymethylmethacrylate), ABS (acrylonitrile-butadiene-styrene terpolymer), PS (polystyrene), PVC (polyvinylchloride), crystalline thermoplastic resins including PFA (perfluoroalkoxyalkane), MFA (co-polymer of TFE (tetrafluoroethylene) and PFVE (perfluorinated vinyl ether)), FEP (fluorinated ethylene propylene polymers), PPS (polyphenylene sulfide), PEK (polyether ketone), PEEK (polyether-ether ketone), ECTFE (ethylene-chlorotrifluoroethylene copolymer), PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PET (polyethylene terephthalate), POM (polyacetal), PA (polyamide), UHMW-PE (ultra high molecular weight polyethylene), PP (polypropylene), PE (polyethylene), HDPE (high density polyethylene), LDPE (low density polyethylene), and advanced engineering resins such as PBI (polybenzimidazole), poly(ether sulfone), poly(aryl sulfone), polyphenylene ethers, polybenzoxazoles, and polybenzothiazoles, as well as blends and co-polymers thereof.

Measured CTE's of the films may be an inherent property of the material by virtue of the materials chemical make-up. Alternatively, the CTE may be significantly lower than the inherent CTE of the film material through the use of additives and or by the performance of additional processing steps. The CTE of the solvent cast film can be any CTE which is below 70 ppm/° C., specifically below 60 ppm/° C., and allows the film to function in its intended utility. For example, for a flexible circuit board the CTE can be close enough to that of the adjacent metallic conductive layer that the film is capable of serving its intended utility as a dielectric substrate, a layer in a laminate and/or a covering for a flexible circuit board. In separate embodiments, the CTE is less than 70 ppm/° C., less than 50 ppm/° C., less than 40 ppm/° C., less than 35 ppm/° C., less than 30 ppm/° C., or less than 20 ppm/° C. According to other embodiments, the film has a CTE of at least 5 ppm/° C. The film can also have a CTE of 5 ppm/° C. to 60 ppm/° C., and more specifically the coefficient of thermal expansion is 10 ppm/° C. to 30 ppm/° C., and even more specifically 10 ppm/° C. to 20 ppm/° C.

Alternatively, the CTE of the film is adjusted to match a substrate material on which it is disposed. In one embodiment, the film has a CTE that is within ±20 ppm/° C. of the CTE of copper, silicon, aluminum, gold, silver, nickel, a glass, a ceramic, or a polymer, specifically within ±20 ppm/° C. of the CTE of copper, silicon, aluminum, gold, silver, or nickel. In another embodiment, the film has a CTE that is within ±15 ppm/° C. of the coefficient of thermal expansion of copper, silicon, aluminum, gold, silver, or nickel, specifically copper.

In an advantageous feature, it has been found that the CTE of the films is very stable. For example, the film after lamination to a substrate at a temperature from 250 to 450° C. has a CTE within ±10 ppm/° C. of the CTE of the film prior to lamination.

The thickness of the films can vary widely depending upon the end use application, the method of making the film, the solids contents of the casting solution, to name a few of the subject parameters. The thickness may vary from 0.1 micrometers up to 10,000 micrometers, or more particularly from 5 micrometers up to 1,000 micrometers, however it is expected that for use in flexible circuit boards the most likely thickness will be between 0.1 micrometers and 250 micrometers.

The final solvent cast film may contain residual solvent and still be capable of functioning for its intended purpose. The minimum amount of residual solvent will be the most residual solvent content under which the film will still function for its intended utility. One the other hand, the solvent cast films may also contain as low a residual solvent content as is possible to achieve. For example, solvent is expensive and can be an environmental hazard. Both a cost savings and an improvement of environmental conditions may be achieved by minimizing the amounts of solvent contained in final product. The residual solvent content will be less than 5% of the total weight of the film. In another embodiment, the amount of residual solvent will be less than 1% of the total weight of the film.

Solvents which can be used in the process include any solvent with which a solvent cast film may be made. The solvent can be a good solvent for polyimides, by for example, having a relatively high boiling to facilitate solution film formation or direct devolatization via extrusion. The solvent for film formation can be the same that is used to make the polyamic acid solution described below. Examples of suitable solvents include, but are not limited to, N-methylpyrrolidinone (NMP), trichloroethane, N,N-dimethylacetamide (DMAc), N-methylpyrrolidinone (NMP), dimethylsulfoxide (DMSO), sulfolane, tetrahydrofuran (THF), benzophenone, cyclohexanone, phenol, mixtures of o-, p- and m-cresols, mixtures of cresylic with phenol, ethylphenols, isopropylphenols, tert-butylphenols, xylenols, mesitols, chlorophenols, dichlorophenols, such as ortho-dichlorobenzene (o-DCB), phenylphenols, a monoalkyl ether of ethylene glycol having from 1 to 4 carbon atoms in the alkyl group, a monoalkyl ether of diethylene glycol having from 1 to 4 carbon atoms in the alkyl group, a monoaryl ether glycol, a monoaryl ether of propylene glycol, N,N-dimethylformamide, tetramethylurea, phenoxy ethanol, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, N-cyclohexylpyrrolidinone, ethyl lactate, an ionic liquid, and mixtures containing one or more of these solvents. Ionic liquids generally include salts having a melting point that is relatively low (below 100° C.). Examples of ionic liquids include, but and are not limited to ammonium, imidazolium-, phosphonium-, pyridinium-, pyrrolidinium-, and sulfonium-based salts. Counter-ions in such liquids can include, but are not be limited to the following: bromides, chlorides, tetrafluoroborates, acetates, phosphates, carbonates, sulfates, methane sulfates, nitrates, thiocyanates, and combinations thereof.

The skilled artisan will appreciate that the specific solvent used is dependent on any number of factors including the solubility of the polyimide and the precursor monomers in a solvent, and the volatility of the solvent, for example.

Solvent cast films according to the present invention may be made by any method known in the art. The following patents assigned to GE disclose generic methods of making solvent cast films and casting solutions: U.S. Pat. Nos. 4,115,341; 4,157,996; 4,307,226; 4,360,633; 4,374,972; and, 3,847,867. One manufacturing process can involve the following steps: forming a polyamic acid solution comprising a monomer component comprising one or more dianhydrides and one or more organic diamines at least partially dissolved in a solvent system; casting the polyamic acid solution onto a substrate such that the polyamic acid solution takes on a form having a length, width and depth on the surface of the substrate; removing the solvent, and curing the polyamic acid solution to form a film having a CTE less than 70 ppm/° C., specifically less than 60 ppm/° C., and a thickness of from 0.1 micrometers to 250 micrometers, specifically 5 to 250 micrometers.

Alternately, the method can comprise making a solvent cast film comprising: preparing a casting solution comprising a polyamic acid solution made up of a monomer component and a solvent component; casting a film of the casting solution on a support base; removing solvent from the cast film for a predetermined period of time to form a solvent cast film having a CTE less than 70 ppm/° C., specifically less than 60 ppm/° C. and a thickness of between 5 micrometers and 250 micrometers, specifically between 0.1 and 250 micrometers; and conducting an additional process step on the solvent cast film to reduce the CTE of the film below 30 ppm/° C.

The polyamic acid solution may be prepared by mixing one or more dianhydride(s), water, and solvent as by stirring until the one or more dianhydride component is dissolved. Then the one or more monomeric diamine can be added and the solution stirred until the amines dissolve. The components which make up the dianhydride component and the diamine component may include 1, 2, 3, 4, 5, or more different dianhydrides and diamines. The scope of the present invention is specifically intended to include all permutations, and combinations of the number and variety of dianhydride and diamine monomers. For example, in one embodiment, the polyamic acid solution will be made up of two different dianhydrides and two different diamines. In another embodiment, one of the one or more dianhydrides is ODPA.

In general, the organic amine component may be included in an amount of from 0.5 mole to 2.0 moles, or, more particularly, from 1 to 1.3 moles, per mole of dianhydride component. Where more than one compound is included in a component of the present solution, the parts, moles, or other quantity of such component is taken as the sum of the parts, moles, or such other quantity, respectively, of each compound included in such component. Thus, for example, total amine content is calculated by adding the equivalent amounts of each diamine in the amine component e.g., 2(number of moles of 1^(st) diamine)+2(number of moles of 2^(nd) diamine)=total equivalents of amine.

Total anhydride content is calculated in a similar fashion. A slight excess of amine is can be used to impart additional film flexibility or possible cross-linking. It has been found that polyimide enamel can have from 5 to 500 repeating dianhydride-diamine reaction product units and preferably from 10 to 200. Terminal amino and phthalic acid or phthalic anhydride or various suitable end groups can also be present.

Experience has shown that sufficient solvent should be utilized to provide a solids content to provide a solution with a workable viscosity for stirring and handling. In one embodiment, the solids content will be from 1-65% by weight. In other embodiments the solids content will be from 1-40%, 1-25%, 1-15%, or 1-12.5% by weight.

Solutions having high ratios of monomeric reactants to organic solvent component advantageously minimize the amount of organic solvent released during subsequent formation and cure of polyetherimide resins as in the manufacture of solvent cast film. Such solutions having high amounts of monomeric reactants may have higher viscosities than desired for some solvent cast films. Typically, inclusion of water decreases the solution viscosity. A given decrease in viscosity may be effected using a lower amount of added water relative to the amount of added organic solvent component which would be required to effect the same viscosity decrease.

Water may or may not be a part of the polyamic acid solution. Water may be present in any amount up to the maximum amount at which the solution is substantially free of precipitate. Although water is miscible with the organic solvent component in substantially all proportions, inclusion of too much water in the present monomeric solution results in precipitate or other plural phase formation. The amount of water which may be present depends on the particular dianhydride and diamine components, the particular organic solvent component, and the weight ratio of monomeric reactants to organic solvent.

Advantageously, the present polyamic acid solutions may include the monomeric reactants in a combined amount of 40 or more weight percent, e.g. from 40 to 75 or more weight percent, based on the weight of the solution. In general, such high monomer content solutions, including water as may be required, have suitable viscosities in the temperature range, e.g., 15° C. to 200° C., normally used to make solvent cast films.

Solutions including water are more easily prepared by adding the monomeric reactant components with stirring to a solution of the water and organic solvent component. Preparation of the solution is generally accelerated at elevated temperatures.

An additive can present in the polyimide films, for example by adding to the polyamic acid solutions in order to reduce the CTE below the CTE that the material would have without the additive. These additives include those which will aid in lowering the CTE of the solvent cast film, and those which can aid in producing another desirable property in the present films. These ingredients may be used in any amount to impart the desired property at proportions of from 0.001 to 60 parts of additive, per 100 parts by weight of polyimide. Alternatively these additives may be added in amounts from 0.01 to 30 parts of additive, and more particularly from 0.1 to 10 parts of additive per 100 parts by weight of polyimide.

The types of additives which can be employed to lower the CTE of a solvent cast polyimide film include modified nano-composite silicates (nanoclays) and soluble nano-particle precursors such as aluminum(acetylacetonate)₃.

A nanoclay can be added directly to the polyamic acid composition after it is formed. It has also been found that polyimide can be readily solubilized in an exfoliated nanocomposite solution, and that exfoliation can be maintained after removal of the solvent by devolatization or precipitation into nonsolvent. The resulting polyimide-nanocomposite materials can be formed into films via solution casting or melt extrusion. The resulting films have high Tg and low CTE. In some cases, the Tg is the same as a film of the same composition without the nanoclay. The films containing the nanoclay can also be transparent.

Moreover, it has been found that polymerization of a diamine and dianhydride in the presence of organically modified silicates results in good dispersion of the modified nanofiller. The nanofilled polyimide composite can be formed into films by melt extrusion or solution casting to give a low CTE, high Tg, polyimide film.

Exfoliated nanoclays are most commonly used. Exfoliation, e.g., by sonication of organically modified nanosilicates, is carried out in a solvent system. For example exfoliating is carried out in a composition comprising from 10 to 90% by weight of the nanoclay and from 10 to 90% by weight of the solvent system. Exfoliation can be performed before addition to the polyamic acid solution, after addition to the polyamic acid solution, or before reacting the dianhydride component and the organic diamine component in the solvent system. Alternatively, addition of a high molecular weight polymer to the exfoliated nanosilicate solution results in exfoliated high Tg nanocomposites. These materials can be formed into films by solution casting to give a low CTE polyimide film. In one embodiment homogenization of the modified nanosilicate in the selected solvent is followed by sonication. Sonication can be performed in either a batch or continuous process. In the batch process, the homogenized modified silicate/solvent mixture is placed in contact with the sonic source. The mixture is stirred well to ensure uniform sonication of the entire mixture. In the continuous process, the modified nanosilicate/solvent mixture is flowed through the sonic zone at a given rate. The modified nanosilicate/solvent mixture is stirred well to ensure a uniform dispersion of the nanosilicate. In either the batch or continuous process, the sonication conditions required for exfoliation (i.e. flow rate, sonication power, sonication time) depends on the type of modifier used, solvent, batch size, configuration and size of the sonic source, and temperature at which sonication takes place. Intercalation and exfoliation of the nanosilicate particles can be observed via X-ray diffraction (XRD) of the resulting solution. Exfoliation can be more directly observed by combining the sonicated nanosilicate solution with a polyimide solution, removing the solvent by evaporation or precipitation, casting or pressing a film and performing TEM analysis.

The nanosilicates may be exfoliated such that the materials d-spacing is greater than the material would have, but for the exfoliation step. According to the present invention the d-spacing can be any that is greater than the unmodified nanosilicate that will lower the CTE of the polyimide film. According to alternate embodiments, the modified nanosilicates will have d-spacings greater than 15, 20, 25, 30, 40, 40, and 75 Angstroms.

The nanosilicate can have an organic modifier with cationic functionality and may be thermally stable at film forming processing temperatures.

It has been found that use of nanoclays, particularly exfoliated nanoclays provides unexpected advantages. Films comprising a nanoclay can have a lower CTE than a film of the same composition without the nanoclay. Alternatively, or in addition, films comprising a nanoclay can have a Tg that is the same as a film of the same composition without the nanoclay. A film comprising a nanoclay can also be transparent. The amount of nanoclay used in the film will vary, depending on the desired film properties. For example, the film can comprise from 0.1 to 10 wt % nanoclay, specifically 1 to 10 wt % nanoclay, based on the total weight of the film.

A general methodology for making solvent cast films according to this process involves dispersing the modified clay either by sonication or high shear mixing in the chosen solvent (for example, DMAc). The clay dispersion is formulated to be in the range of 1 to 15% solids by weight, or more particularly, 1 to 5% solids by weight. The monomers, at least one dianhydride monomer and at least one diamine monomer, are added to the clay dispersion to form a modified polyamic acid solution. Also, instead of adding polyamic acid to the clay dispersion, fully imidized soluble polyimides can be dissolved in solvents such as DMAc and NMP in the range of 5-25% solids by weight. In another embodiment, a 10 wt % solution of the dried film in dimethylacetamide or N-methylpyrrolidinone has an inherent viscosity of greater than 0.05 dl/g. The polyimide solution can then be combined with the clay dispersion and cast as above.

Another additive that can be employed to lower the CTE of solvent cast polyimide films are metal oxide nanoparticles, which can be formed from an organo-metallic precursor. Metal oxide nanoparticles can be generated in situ by decomposing an organometallic precursor. One example of such a material is aluminum(acetylacetonate)₃ (Al(acac)₃). Thermolysis of (Al(acac)₃) yields aluminum oxide. When done in dilute solution (small molecule solvent or polymer melt) Al₂O₃ nanoparticles are formed. Targeting a 1% by weight loading of Al₂O₃ in the final polymer, the precursor can be added upfront to the polymerization of dianhydride and diamine monomers, specifically oxydiphthalic anhydride and diaminodiphenylsulfone. Resultant polymer filled with Al₂O₃ nanoparticles exhibited a CTE lowered by more than 15% compared to an unfilled control sample.

In addition to the organo-metallic precursor being added to the polymerization, the precursor can be solvent blended with the polyamic acid solution, or finished soluble polyimide, or blended and extruded with finished polymer to yield a filled system. The materials in solution can be cast as films and cured to give the filled film. Other suitable organo-metallic precursors include metal(acac) complexes, and ceramic precursors such as molybdenum sulfide.

Other classes of additives which can be used to impart a desirable property other than, or in addition to lowering the CTE of a polyimide film, include fillers and reinforcements for example fiber glass, milled glass, glass beads, flake and the like. Minerals such as talc, wollastonite, mica, kaolin, or montmorillonite clay, silica, fumed silica, perlite, quartz, and barite may be added. The compositions can also be modified with effective amounts of inorganic fillers, such as, for example, carbon fibers and nanotubes, glass fibers, metal fibers, metal powders, conductive carbon, and other additives including nano-scale reinforcements.

In some cases a metal oxide may be added to the polymers of the present invention. In some instances the metal oxide may further improve flame resistance (FR) performance by decreasing heat release and increasing the time to peak heat release. Titanium dioxide is of note. Other metal oxides include zinc oxides, boron oxides, antimony oxides, iron oxides, and transition metal oxides. Metal oxides that are white may be desired in some instances. Metal oxides may be used alone or in combination with other metal oxides. Metal oxides may be used in any effective amount, in some instances at from 0.01 to 20% by weight of the polymer.

Other useful additives include smoke suppressants such as metal borate salts, for example zinc borate, alkali metal or alkaline earth metal borate or other borate salts. Additionally other boron containing compounds, such as boric acid, borate esters, boron oxides, or other oxygen compounds of boron may be useful. Additionally other flame retardant additives, such as aryl phosphates and brominated aromatic compounds, including polymers containing linkages made from brominated aryl compounds, may be employed. Examples of halogenated aromatic compounds are brominated phenoxy resins, halogenated polystyrenes, halogenated imides, brominated polycarbonates, brominated epoxy resins and mixtures thereof.

In some instances it maybe desired to have flame retardant compositions that are essentially free of halogen atoms, especially bromine and chlorine. Essentially free of halogen atoms means that in some embodiments the composition has less than 3% halogen, specifically chlorine and/or bromine by weight of the composition, and in other embodiments less than 1% by weight of the composition contains halogen atoms, specifically chlorine and/or bromine. The amount of halogen atoms can be determined by ordinary chemical analysis.

The composition may also optionally include a fluoropolymer in an amount of 0.01 to 5.0% fluoropolymer by weight of the composition. The fluoropolymer may be used in any effective amount to provide anti-drip properties to the resin composition. Some examples of suitable fluoropolymers and methods for making such fluoropolymers are set forth, for example, in U.S. Pat. Nos. 3,671,487, 3,723,373 and 3,383,092. Suitable fluoropolymers include homopolymers and copolymers that comprise structural units derived from one or more fluorinated alpha-olefin monomers. The term “fluorinated alpha-olefin monomer” means an alpha-olefin monomer that includes at least one fluorine atom substituent. Some of the suitable fluorinated alpha-olefin monomers include, for example, fluoroethylenes such as, for example, CF₂═CF₂, CHF═CF₂, CH₂═CF₂, and CH₂═CHF and fluoro propylenes such as, for example, CF₃CF═CF₂, CF₃CF═CHF, CF₃CH═CF₂, CF₃CH═CH₂, CF₃CF═CHF, CHF₂CH═CHF, and CF₃CF═CH₂.

Some of the suitable fluorinated alpha-olefin copolymers include copolymers comprising structural units derived from two or more fluorinated alpha-olefin monomers such as, for example, poly(tetrafluoro ethylene-hexafluoro ethylene), and copolymers comprising structural units derived from one or more fluorinated monomers and one or more non-fluorinated monoethylenically unsaturated monomers that are copolymerizable with the fluorinated monomers such as, for example, poly(tetrafluoroethylene-ethylene-propylene) copolymers. Suitable non-fluorinated monoethylenically unsaturated monomers include for example, alpha-olefin monomers such as, for example, ethylene, propylene, butene, acrylate monomers such as for example, methyl methacrylate, butyl acrylate, and the like, with poly(tetrafluoroethylene) homopolymer (PTFE) preferred.

Other additives which may be added to the solvent cast films include antioxidants such as phosphites, phosphonites, and hindered phenols. Phosphorus containing stabilizers, including triaryl phosphite and aryl phosphonates, are of note as useful additives. Difunctional phosphorus containing compounds can also be employed. Stabilizers with a molecular weight of greater than or equal to 300 Daltons are preferred. In other instances phosphorus containing stabilizers with a molecular weight of greater than or equal to 500 Daltons are useful. Phosphorus containing stabilizers are typically present in the composition at 0.05-0.5% by weight of the formulation. Colorants as well as light stabilizers and UV absorbers may also be used. Flow aids and mold release compounds are also contemplated. Examples of mold release agents are alkyl carboxylic acid esters, for example, pentaerythritol tetrastearate, glycerin tri-stearate and ethylene glycol distearate. Mold release agents are typically present in the composition at 0.05-0.5% by weight of the formulation. Preferred mold release agents will have high molecular weight, typically greater than 300 Daltons, to prevent loss if the release agent from the molten polymer mixture during melt processing.

Compositions used to form the articles according to the present invention may also include various additives such as nucleating, clarifying, stiffness, and/or crystallization rate agents. These agents are used in a conventional matter and in conventional amounts.

The compositions can be blended with the aforementioned ingredients by a variety of methods involving intimate admixing of the materials with any additional additives desired in the formulation. A preferred procedure includes solution blending, although melt blending may be employed after the solvent cast film is made. Illustrative examples of equipment used in such melt processing methods include co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disc-pack processors, and various other types of extrusion equipment.

Liquid coating solutions can be formed using the above-described polyimide compositions, as well as film-forming solutions. The liquid coating solutions have many and varied uses. The coating solutions can be applied to a variety of substrates using any suitable coating method, e.g. dipping, brushing, spraying, wiping and the like, and thereafter heated to evaporate the solvent system and form cured polyetherimide resinous coatings. The temperature is preferably increased gradually to produce smooth resinous coatings. The polymerization and cure proceeds advantageously at a temperature of from 125° C. to 300° C. or more.

The polyamic acid solution can also be used as a coating solution which may be applied immediately upon preparation or stored prior to use. In general, maximum storage life can be obtained by storing the solutions under a nitrogen blanket in the absence of light.

Polymers used to make the solvent cast films and coatings are polyimides and in some specific instances, polyetherimides. Polyimides according to the present invention have the general formula (1):

wherein a is more than 1, typically 10 to 1,000 or more, or more specifically 10 to 500; and wherein V is a tetravalent linker without limitation, as long as the linker does not impede synthesis or use of the polyimide. Suitable linkers include but are not limited to: (a) substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, (b) substituted or unsubstituted, linear or branched, saturated or unsaturated alkyl groups having 1 to 30 carbon atoms; or combinations comprising at least one of the foregoing. Suitable substitutions and/or linkers include, but are not limited to, ethers, epoxides, amides, esters, and combinations comprising at least one of the foregoing. At least a portion of the linkers V contain a portion derived from a bisphenol. Desirably linkers include but are not limited to tetravalent aromatic radicals of structures (2):

wherein W is a divalent moiety including —O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— (y being an integer from 1 to 5), and halogenated derivatives thereof, including perfluoroalkylene groups, or a group of the formula —O—Z—O— wherein the divalent bonds of the —O— or the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions, and wherein Z includes, but is not limited, to divalent radicals of formulas 3:

wherein Q includes but is not limited to a divalent moiety including —O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— (y being an integer from 1 to 5), and halogenated derivatives thereof, including perfluoroalkylene groups.

R in formula (1) includes but is not limited to substituted or unsubstituted divalent organic radicals such as: (a) aromatic hydrocarbon radicals having 6 to 20 carbon atoms and halogenated derivatives thereof; (b) straight or branched chain alkylene radicals having 2 to 20 carbon atoms; (c) cycloalkylene radicals having 3 to 20 carbon atoms, or (d) divalent radicals of the general formula (4):

wherein Q includes but is not limited to a divalent moiety including —O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— (y being an integer from 1 to 5), and halogenated derivatives thereof, including perfluoroalkylene groups.

Exemplary classes of polyimides include polyamidimides and polyetherimides, particularly those polyetherimides which are melt processible, such as those whose preparation and properties are described in U.S. Pat. Nos. 3,803,085 and 3,905,942.

Exemplary polyetherimide resins comprise more than 1, typically 10 to 1,000, or more specifically, 10 to 500 structural units, of the formula (5):

wherein T is —O— or a group of the formula —O—Z—O— wherein the divalent bonds of the —O— or the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions, and wherein Z includes, but is not limited, to divalent radicals of formula 10 as defined above.

In one embodiment, the polyetherimide may be a copolymer which, in addition to the etherimide units described above, further contains polyimide structural units of the formula (6):

wherein R is as previously defined for formula (6) and M includes, but is not limited to, the following radicals:

The polyetherimide can be prepared by various methods, including, but not limited to, the reaction of an aromatic bis(ether anhydride) of the formula (7):

with an organic diamine of the formula (8): H₂N—R—NH₂  (8) wherein R and T are defined in relation to formulas (1) and (5).

Examples of specific aromatic bis(ether anhydride)s and organic diamines are disclosed, for example, in U.S. Pat. Nos. 3,972,902 and 4,455,410. Illustrative examples of dianhydride molecules include:

-   2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; -   4,4′-bis(3,4-dicarboxyphenoxy)diphenylether dianhydride; -   4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride; -   4,4′-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; -   4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride; -   2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; -   4,4′-bis(2,3-dicarboxyphenoxy)diphenylether dianhydride; -   4,4′-bis(2,3-dicarboxyphenoxy)diphenylsulfide dianhydride; -   4,4′-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; -   4,4′-bis(2,3-dicarboxyphenoxy)diphenylsulfone dianhydride; -   4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane     dianhydride; -   4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenylether     dianhydride; -   4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenylsulfide     dianhydride; -   4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)benzophenone     dianhydride; -   4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenylsulfone     dianhydride; -   1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride; -   1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride; -   1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride; -   1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride; -   3,3′,4,4′-diphenyl tetracarboxylic dianhydride; -   3,3′,4,4′-benzophenonetetracarboxylic dianhydride; -   naphthalic dianhydrides, such as 2,3,6,7-naphthalic dianhydride,     etc.; -   3,3′,4,4′-biphenylsulphonictetracarboxylic dianhydride; -   3,3′,4,4′-biphenylethertetracarboxylic dianhydride; -   3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride; -   4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride; -   4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulphone dianhydride; -   4,4′-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride; -   3,3′,4,4′-biphenyltetracarboxylic dianhydride; -   bis(phthalic)phenylsulphineoxide dianhydride; -   p-phenylene-bis(triphenylphthalic)dianhydride; -   m-phenylene-bis(triphenylphthalic)dianhydride; -   bis(triphenylphthalic)-4,4′-diphenylether dianhydride; -   bis(triphenylphthalic)-4,4′-diphenylmethane dianhydride; -   2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; -   4,4′-oxydiphthalic dianhydride; -   pyromellitic dianhydride; -   3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride; -   4′,4′-bisphenol A dianhydride; -   hydroquinone diphthalic dianhydride; -   6,6′-bis(3,4-dicarboxyphenoxy)-2,2′,3,3′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indene]dianhydride; -   7,7′-bis(3,4-dicarboxyphenoxy)-3,3′,4,4′-tetrahydro-4,4,4′,4′-tetramethyl-2,2′-spirobi[2H-1-benzopyran]dianhydride; -   1,1′-bis[1-(3,4-dicarboxyphenoxy)-2-methyl-4-phenyl]cyclohexane     dianhydride; -   3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride; -   3,3′,4,4′-diphenylsulfidetetracarboxylic dianhydride; -   3,3′,4,4′-diphenylsulfoxidetetracarboxylic dianhydride; -   4,4′-oxydiphthalic dianhydride; -   3,4′-oxydiphthalic dianhydride; -   3,3′-oxydiphthalic dianhydride; -   3,3′-benzophenonetetracarboxylic dianhydride; -   4,4′-carbonyldiphthalic dianhydride; -   3,3′,4,4′-diphenylmethanetetracarboxylic dianhydride; -   2,2-bis(4-(3,3-dicarboxyphenyl)propane dianhydride; -   2,2-bis(4-(3,3-dicarboxyphenyl)hexafluoropropane dianhydride; -   (3,3′,4,4′-diphenyl)phenylphosphinetetracarboxylic dianhydride; -   (3,3′,4,4′-diphenyl)phenylphosphineoxidetetracarboxylic dianhydride; -   2,2′-dichloro-3,3′,4,4′-biphenyltetracarboxylic dianhydride; -   2,2′-dimethyl-3,3′,4,4′-biphenyltetracarboxylic dianhydride; -   2,2′-dicyano-3,3′,4,4′-biphenyltetracarboxylic dianhydride; -   2,2′-dibromo-3,3′,4,4′-biphenyltetracarboxylic dianhydride; -   2,2′-diiodo-3,3′,4,4′-biphenyltetracarboxylic dianhydride; -   2,2′-ditrifluoromethyl-3,3′,4,4′-biphenyltetracarboxylic     dianhydride; -   2,2′-bis(1-methyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic     dianhydride; -   2,2′-bis(1-trifluoromethyl-2-phenyl)-3,3′,4,4′-biphenyltetracarboxylic     dianhydride; -   2,2′-bis(1-trifluoromethyl-3-phenyl)-3,3′,4,4′-biphenyltetracarboxylic     dianhydride; -   2,2′-bis(1-trifluoromethyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic     dianhydride; -   2,2′-bis(1-phenyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic     dianhydride; -   4,4′-bisphenol A dianhydride; -   3,3′,4,4′-diphenylsulfoxidetetracarboxylic dianhydride; -   4,4′-carbonyldiphthalic dianhydride; -   3,3′,4,4′-diphenylmethanetetracarboxylic dianhydride; -   2,2′-bis(1,3-trifluoromethyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic     dianhydride, and all isomers thereof, as well as combinations of the     foregoing.

The bis(ether anhydride)s can be prepared by the hydrolysis, followed by dehydration, of the reaction product of a nitro substituted phenyl dinitrile with a metal salt of a bisphenol compound (e.g., BPA) in the presence of a dipolar, aprotic solvent. An exemplary class of aromatic bis(ether anhydride)s included by formula (7) above includes, but is not limited to, compounds wherein T is of the formula (9):

and the ether linkages, for example, are in the 3,3′, 3,4′, 4,3′, or 4,4′ positions, and mixtures comprising at least one of the foregoing, and where Q is as defined above.

Any diamino compound may be employed. Examples of suitable compounds are:

-   m-phenylenediamine; -   p-phenylenediamine; -   2,4-diaminotoluene; -   2,6-diaminotoluene; -   m-xylylenediamine; -   p-xylylenediamine; -   benzidine; -   3,3′-dimethylbenzidine; -   3,3′-dimethoxybenzidine; -   1,5-diaminonaphthalene; -   bis(4-aminophenyl)methane; -   bis(4-aminophenyl)propane; -   bis(4-aminophenyl)sulfide; -   bis(4-aminophenyl)sulfone; -   bis(4-aminophenyl)ether; -   4,4′-diaminodiphenylpropane; -   4,4′-diaminodiphenylmethane(4,4′-methylenedianiline); -   4,4′-diaminodiphenylsulfide; -   4,4′-diaminodiphenylsulfone; -   4,4′-diaminodiphenylether(4,4′-oxydianiline); -   1,5-diaminonaphthalene; -   3,3′dimethylbenzidine; -   3-methylheptamethylenediamine; -   4,4-dimethylheptamethylenediamine; -   2,2′,3,3′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indene]-6,6′-diamine; -   3,3′,4,4′-tetrahydro-4,4,4′,4′-tetramethyl-2,2′-spirobi[2H-1-benzopyran]-7,7′-diamine; -   1,1′-bis[1-amino-2-methyl-4-phenyl]cyclohexane, and isomers thereof     as well as mixtures and blends comprising at least one of the     foregoing.

Desirably, the diamino compounds are aromatic diamines, especially m- and p-phenylenediamine and mixtures comprising at least one of the foregoing.

In one embodiment, the polyetherimide resin comprises structural units according to formula 12 wherein each R is independently p-phenylene or m-phenylene or a mixture comprising at least one of the foregoing and T is a divalent radical of the formula (10):

Included among the many methods of making the polyimides, particularly polyetherimides, are those disclosed in U.S. Pat. Nos. 3,847,867, 3,850,885, 3,852,242, 3,855,178, 3,983,093, and 4,443,591.

The reactions can be carried out employing solvents, e.g., o-dichlorobenzene, m-cresol/toluene and the like, to effect a reaction between the anhydride of formula (7) and the diamine of formula (8), at temperatures of 100° C. to 250° C. Chain stoppers and branching agents may also be employed in the reaction.

When polyimide copolymers of ether-containing and non-ether containing subunits are used, a dianhydride, such as pyromellitic anhydride, is used in combination with the bis(ether anhydride). The polyimides can optionally be prepared from reaction of an aromatic bis(ether anhydride) with an organic diamine in which the diamine is present in the reaction mixture at less than or equal to 0.2 molar excess. Under such conditions the polyetherimide resin may have less than or equal to 15 microequivalents per gram (μeq/g) acid titratable groups, or, more specifically less than or equal to 10 microequivalents/g acid titratable groups, as shown by titration with chloroform solution with a solution of 33 weight percent (wt %) hydrobromic acid in glacial acetic acid. Acid-titratable groups are essentially due to amine end-groups in the polyetherimide resin.

One route for the synthesis of polyimides proceeds through a bis(4-halophthalimide) having the following structure (11):

wherein R is as described above and X is a halogen. The bis(4-halophthalimide) wherein R is a 1,3-phenyl group (12) is particularly useful.

Bis(halophthalimide)s (11) and (12) are typically formed by the condensation of amines, e.g., 1,3-diaminobenzene with anhydrides, e.g., 4-halophthalic anhydride (13):

Polyetherimides may be synthesized by the reaction of the bis(halophthalimide) with an alkali metal salt of a bisphenol such as bisphenol A or a combination of an alkali metal salt of a bisphenol and an alkali metal salt of another dihydroxy substituted aromatic hydrocarbon in the presence or absence of phase transfer catalyst. Suitable phase transfer catalysts are disclosed in U.S. Pat. No. 5,229,482. Suitable dihydroxy substituted aromatic hydrocarbons include those having the formula (14): HO-A²-OH  (14) wherein A² is a divalent aromatic hydrocarbon radical. Suitable A² radicals include m-phenylene, p-phenylene, 4,4′-biphenylene, and similar radicals.

As described above, virgin polyimides can be used in the formation of the solvent cast polyimide films. However, in a specific embodiment, the polyimide films comprise up to 50 wt %, specifically up to 30 wt %, of a recycled polyimide, wherein prior to recycling the recycled polyimide film has a glass transition temperature from 210° C. to 450° C. In one embodiment, virgin polyimide is melt blended with recycled polyimide, for example polyimide that has already been formed into a film. In another embodiment, virgin polyimide is solvent mixed with recycled polyimide, for example polyimide that has been formed into a film as described above. Polyimide compositions comprising the recycled polyimide can then be formed into a casting composition and be cast as described herein, for example from a composition comprising 1 to 30 wt % solids. In the foregoing embodiments, the CTE of the film comprising the recycled polyimide can be within ±10 ppm/° C. of a film having the same composition without the recycled polyimide.

As an alternative to creating a solvent cast film having a CTE less than 70 ppm/° C., in another embodiment less than 60 ppm/° C., or in another embodiment, less than 35 ppm/° C., it is possible to add an additional process step to lower the CTE of a solvent cast film having a CTE above 70 ppm/° C., above 60 ppm/° C., or in another embodiment, above 35 ppm/° C., to a CTE below 60 ppm/° C. and in another embodiment less than 35 ppm/° C., specifically less than 30 ppm/° C.

The CTE of a solvent cast film can be reduced by biaxially stretching as described in U.S. Pat. No. 5,460,890. Similarly, the CTE of a melt extruded film or fully imidized solvent cast film can be reduced by thermally biaxially stretching as described in U.S. Pat. No. 5,260,407. The skilled artisan will be familiar with the other known methods of lowering the CTE of a polyimide film.

For example, a film with a low in-plane CTE may be obtained from polyimide resin compositions because the resin exhibits a partial crystallinity after annealing, and the crystalline phases can be aligned in two dimensions through biaxial stretching after extrusion. The film can then be heat set while constrained in a frame, returning the amorphous portion of the film back to a random unoriented configuration while retaining the alignment of the crystalline phases (and also inducing more aligned crystalline domains). The alignment of the crystalline phases results in a film with a low CTE. Since the amorphous part of the material is returned to its random state the film will not exhibit shrinkage, even when taken above the Tg of the material. This can lead to a dimensionally stable film at flex fabrication temperatures, because the crystalline domains are stable to temperatures above 400° C. The film has high temperature survivability due to the high Tg of the material and the partial crystallinity. The Tg of the material is above the temperature of the solder float test, which makes the material survive this test as well. The polymer crystals do not melt until temperatures exceeding 400° C., which is well above the temperatures seen during flex fabrication. The crystals act as effective crosslinks below Tm, holding the material together for high temperature survivability. The crystallization kinetics of the composition identified below is fairly slow, allowing the material to be melt extruded to a film before significant crystallization takes place. The film can then be heat set above Tg to induce crystallinity.

A wide range of polyetherimide copolymers containing a combination of the monomers 4,4′-oxydiphthalic anhydride (ODPA), bisphenol A dianhydride (BPADA), meta-phenylenediamine (mPD), and para-phenylenediamine (pPD) exhibit the partial crystallinity and high heat necessary for the film to exhibit the desired properties. The polymer can be end capped with, for example, aniline. The scope of the present invention is specifically intended to encompass the monomers and endcaps necessary to have partial crystallinity and to maintain processability. A specific example can be 80-100% ODPA as the dianhydride and 30-100% pPD as the diamine, with 3.5-5% aniline as the endcapping agent.

Varying these compositions can alter the crystallization kinetics to achieve the desired balance of processability and achievable crystallinity to reduce CTE. In one embodiment, the optimum composition in terms of processability, ductility, slow crystallization kinetics, and maximum achievable crystallinity is a dianhydride component comprising 95% ODPA and 5% BPADA, on an equivalents basis, and a diamine component comprising 70% mPD and 30% pPD on an equivalents basis, together with 5% aniline, based on the total equivalents of dianhydride component and diamine component.

Very good film properties are obtained when a specific combination of dianhydrides are used, especially when the specific dianhydrides are used in combination with specific diamines. In one embodiment, the dianhydrides comprise 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4′-oxydiphthalic anhydride, and combinations thereof. Other, additional dianhydrides can be present to adjust the properties of the films. In one embodiment, however, the polyimide has less than 15 molar % of structural units derived from a member of the group consisting of biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, an ester of biphenyltetracarboxylic acid, and combinations thereof.

Alternatively, the polyimides are formed from a dianhydride component that consists essentially of 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4′-oxydiphthalic anhydride, and combinations thereof. In still another embodiment, the polyimides are formed from a dianhydride component that consists of 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4′-oxydiphthalic anhydride, and combinations thereof.

It has further been found films having excellent properties are obtained when the diamine component comprises 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, p-phenylenediamine, 4,4′-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, and combinations thereof. In one embodiment, the diamine component consists essentially of 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, p-phenylenediamine, 4,4′-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, and combinations thereof. In another embodiment, the diamine component consists of 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, p-phenylenediamine, 4,4′-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, and combinations thereof, and no other diamines are present.

The polyimides are further advantageously formed from structural units wherein the diamine component comprises greater than or equal to 10 mole % of 4,4′-diaminodiphenyl sulfone, based on the total moles of diamine component. In one embodiment the diamine component comprises 10 to 100 mole % of 4,4′-diaminodiphenyl sulfone.

The films can have a number of advantageous properties, in addition to low CTE, useful Tg, and low solvent retention. In one embodiment, the film is stable, that is, loses less than 5% of its initial weight after storage in water for 24 hours at 25° C., specifically less than 2% of its initial weight after storage in water for 24 hours at 25° C.

In an unexpected feature, it has been found by the inventors that the polyimides, in particular polyetherimides comprising units derived from specific diamines, can be formulated to exhibit a relatively constant CTE while achieved a Tg from 220 to 375° C. This result is unexpected because ordinarily in thermoplastic amorphous films, CTE varies with Tg of in a linear relationship. It is therefore possible to select a desired Tg while maintaining a specific CTE.

The liquid coating solutions, film casting solutions, coatings, and solvent cast films of the present invention have many and varied uses. The coating solutions may be applied to a variety of substrates using any suitable coating method, e.g. dipping, brushing, spraying, wiping and the like, and thereafter heated to evaporate the solvent system and form cured polyimide resinous coatings and/or solvent cast films. The temperature is preferably increased gradually to produce smooth resinous coatings. The polyimide-forming reaction proceeds advantageously at a temperature of from 125° C. to 450° C. or more. A variety of substrates can be used, for example copper, silicon, aluminum, gold, silver, nickel, a glass, a ceramic, and a polymer, including a polymeric release layer. A first and a second substrate having the same or different compositions can be disposed on opposite sides of the solvent cast polyimide film.

In one embodiment, the coating and casting solutions are used to manufacture a laminate comprising the solvent cast polyimide film, a conductive layer comprising a metal, wherein a side of the film is adheringly disposed on a side of the conductive layer. The conductive metal can be copper, silver, gold, aluminum, or an alloy comprising at least one of the foregoing metals. In a specific embodiment, the metal is copper and wherein the solvent cast film has a coefficient of thermal expansion less than 35 ppm/° C.

In another embodiment, the present coating and casting solutions may be employed to manufacture films for circuit boards, including flexible circuit boards. In this embodiment, a solvent cast polyimide film is adheringly disposed on an electrically conductive substrate, for example a face of a metal layer such as copper, wherein the metal is etched to provide a circuit. A second substrate, e.g., another layer of a conductive metal such as copper, silicon, aluminum, gold, silver, or nickel, can be disposed on a side of the film opposite the first substrate. The flexible printed circuit can further comprise a dielectric layer comprising a second dielectric material other than the polyimide of the film.

Other specific articles that can be manufactured using the solvent cast polyimide films include capacitors, which in their simplest embodiment comprise a solvent cast polyimide film disposed between two electrically conductive layers, e.g., two copper layers.

In still another embodiment, the solutions can be used as wire enamels to form resinous insulating coatings on copper and aluminum wire. In this embodiment, the polyimide film forms a coating on an electrically conductive wire that surrounds at least a portion of the radial surface of the wire.

The solutions can also be used as varnishes for coating or impregnating various substrates such as coils of previously insulated wire (e.g. in motor and generator coils), as well as woven and non-woven fabrics, and the like. The solvent cast films of the present invention may also be used for flexible printed circuit board (FPC), chip-on-flex (COF), and tape automated bonding (TAB) applications. The term “articles” can also include speaker cones, tapes and labels, wire wraps, etc.

EXAMPLES

Without further elaboration, it is believed that the skilled artisan can, using the description herein, make and use the present invention. The following examples are included to provide additional guidance to those skilled in the art of practicing the claimed invention. These examples are provided as representative of the work and contribute to the teaching of the present invention. Accordingly, these examples are not intended to limit the scope of the present invention in any way. Unless otherwise specified below, all parts are by weight and all temperatures are in degrees Celsius.

Materials

ODPA is a dianhydride monomer also known as 4,4′-oxydiphthalic anhydride which can be made as described in U.S. Pat. No. 6,028,203, U.S. Pat. No. 4,870,194, or U.S. Pat. No. 5,021,168.

BPDA is a dianhydride monomer also known as 3,3′,4,4′-biphenyltetracarboxylic dianhydride, which is commercially available from Chriskev Company, with offices in Leawood, Kans.

PMDA is a dianhydride monomer also known as pyromellitic dianhydride, which is commercially available from Aldrich Chemical Company, with offices in Milwaukee, Wis.

BPADA is a dianhydride monomer also known as 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, which is commercially available from Aldrich Chemical Company, with offices in Milwaukee, Wis.

BTDA is a dianhydride monomer also known as 3,3′-benzophenonetetracarboxylic dianhydride which is commercially available from TCI America, with offices in Portland, Oreg.

BPhDA is a dianhydride monomer also known as 4,4′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride which can be made as described in the Journal of Polymer Science, Polymer Chemistry Edition, 1985, Vol. 23(6), pp. 1759-1769.

DDS is a diamine monomer also known as 4,4′-diamino diphenyl sulfone, which is commercially available from Chriskev Company, with offices in Leawood, Kans.

MPD is a diamine monomer also known as meta-phenylenediamine, which is commercially available from Aldrich Chemical Company, with offices in Milwaukee, Wis.

PPD is a diamine monomer also known as para-phenylenediamine, which is commercially available from Aldrich Chemical Company, with offices in Milwaukee, Wis.

ODA is a diamine monomer also known as 4,4′-oxydianiline, which is commercially available from Chriskev Company, with offices in Leawood, Kans.

1,3,4-APB is a diamine monomer also known as 1,3-bis(4-aminophenoxy)benzene, which is commercially available from Chriskev Company, with offices in Leawood, Kans.

1,3,3-APB is a diamine monomer also known as 1,3-bis(3-aminophenoxy)benzene, which is commercially available from Chriskev Company, with offices in Leawood, Kans.

TPPBr is a phosphonium salt also known as tetraphenylphosphonium bromide, which is commercially available from Fluorochem Ltd., with offices in Old Glossop, United Kingdom.

Sodium montmorillonite is an inorganic layered silicate, which is commercially available from Sud-Chemie, with offices in Dusseldorf, Germany.

Examples 1-72 Film Casting Procedure and Experimental for Examples 1-72

Inventive formulations 1-72 were prepared using the compositions specified in Table 1. The amounts of each monomer were calculated at a stoichiometry of 1 amine for every anhydride with no correction for purity, (corrections for purity can affect the final molecular weight of the polymer and could affect the final performance of the article). A Microsoft Excel spreadsheet calculator was constructed that calculates the grams of each monomer based upon the total grams polymer desired and the monomer feeds of dianhydride and amine. The skilled artisan will appreciate that there are many different ways of ascertaining the correct amount by weight of each ingredient to be used in making the films according to the present invention. It is within the ability of the skilled artisan to calculate the weight amount of ingredients based on the overall stoichiometry and the final percent solids of the reaction mechanism enunciated herein.

Casting Procedure: The correct mole ratios of dianhydride and diamine as shown in Table 1 were weighed on an analytical balance to four decimal place accuracy.

TABLE 1 Dianhydrides Diamines ODPA BPDA BTDA BPhD PMDA BPADA DDS PPD 133 APB 134 APB MPD ODA Ex. Solvent (%) (%) (%) A (%) (%) (%) (%) (%) (%) (%) (%) (%) 1 DMAc 50 0 0 0 0 0 50 0 0 0 0 0 2 DMAc 50 0 0 0 0 0 0 0 50 0 0 0 3 DMAc 50 0 0 0 0 0 0 50 0 0 0 0 4 DMAc 50 0 0 0 0 0 0 0 0 0 50 0 5 DMAc 50 0 0 0 0 0 0 0 0 0 0 50 6 DMAc 40 10 0 0 0 0 0 0 50 0 0 0 7 DMAc 40 10 0 0 0 0 0 0 0 0 50 0 8 DMAc 40 10 0 0 0 0 0 0 0 0 0 50 9 NMP/CH 40 10 0 0 0 0 50 0 0 0 0 0 10 NMP/CH 40 10 0 0 0 0 50 0 0 0 0 0 11 NMP/CH 40 10 0 0 0 0 40 10 0 0 0 0 12 NMP/CH 40 10 0 0 0 0 10 40 0 0 0 0 13 DMAc 45 5 0 0 0 0 0 15 35 0 0 0 14 DMAc 45 0 0 0 5 0 0 15 35 0 0 0 15 DMAc 5 0 0 0 45 0 0 15 35 0 0 0 16 DMAc 45 0 5 0 0 0 0 15 35 0 0 0 17 DMAc 5 0 45 0 0 0 0 15 35 0 0 0 18 DMAc 50 0 0 0 0 0 0 15 35 0 0 0 19 DMAc 5 0 0 0 45 0 0 50 0 0 0 0 20 DMAc 45 5 0 0 0 0 0 50 0 0 0 0 21 DMAc 45 0 0 0 5 0 0 50 0 0 0 0 22 DMAc 45 0 5 0 0 0 0 50 0 0 0 0 23 DMAc 5 0 45 0 0 0 0 50 0 0 0 0 24 DMAc 45 0 5 0 0 0 50 0 0 0 0 0 25 DMAc 5 0 45 0 0 0 50 0 0 0 0 0 26 DMAc 40 10 0 0 0 0 50 0 0 0 0 0 27 DMAc 40 10 0 0 0 0 0 50 0 0 0 0 28 DMAc 40 10 0 0 0 0 40 10 0 0 0 0 29 DMAc 40 10 0 0 0 0 10 40 0 0 0 0 30 DMAc 45 0 0 5 0 0 0 0 50 0 0 0 31 DMAc 45 0 0 5 0 0 50 0 0 0 0 0 32 DMAc 45 0 0 5 0 0 0 15 35 0 0 0 33 DMAc 0 5 0 0 0 45 0 15 35 0 0 0 34 DMAc 0 0 0 0 0 50 0 15 35 0 0 0 35 DMAc 50 0 0 0 0 0 50 0 0 0 0 0 36 DMAc 50 0 0 0 0 0 0 0 0 0 50 0 37 DMAc 50 0 0 0 0 0 0 50 0 0 0 0 38 DMAc 50 0 0 0 0 0 0 0 0 0 0 50 39 DMAc 50 0 0 0 0 0 40 0 0 0 10 0 40 DMAc 50 0 0 0 0 0 40 10 0 0 0 0 41 DMAc 50 0 0 0 0 0 40 0 0 0 0 10 42 DMAc 50 0 0 0 0 0 10 0 0 0 40 0 43 NMP 45 0 0 5 0 0 50 0 0 0 0 0 44 NMP 0 0 0 5 45 0 50 0 0 0 0 0 45 NMP 0 0 45 5 0 0 50 0 0 0 0 0 46 NMP 45 0 0 5 0 0 0 15 35 0 0 0 47 NMP 0 0 0 5 45 0 0 15 35 0 0 0 48 NMP 0 0 45 5 0 0 0 15 35 0 0 0 49 DMAc 50 0 0 0 0 0 0 10 0 0 40 0 50 DMAc 50 0 0 0 0 0 0 0 0 0 40 10 51 DMAc 50 0 0 0 0 0 10 40 0 0 0 0 52 DMAc 50 0 0 0 0 0 0 40 0 0 10 0 53 DMAc 50 0 0 0 0 0 0 40 0 0 0 10 54 DMAc 50 0 0 0 0 0 10 0 0 0 0 40 55 DMAc 50 0 0 0 0 0 0 0 0 0 10 40 56 DMAc 50 0 0 0 0 0 0 10 0 0 0 40 57 DMAc 50 0 0 0 0 0 0 0 0 50 0 0 58 DMAc 50 0 0 0 0 0 40 0 0 10 0 0 59 DMAc 50 0 0 0 0 0 0 0 0 10 40 0 60 DMAc 50 0 0 0 0 0 0 40 0 10 0 0 61 DMAc 50 0 0 0 0 0 0 0 0 10 0 40 62 DMAc 50 0 0 0 0 0 10 0 0 40 0 0 63 DMAc 50 0 0 0 0 0 0 0 0 40 10 0 64 DMAc 50 0 0 0 0 0 0 10 0 40 0 0 65 DMAc 40 10 0 0 0 0 0 10 0 0 40 0 66 DMAc 40 10 0 0 0 0 0 0 0 0 40 10 67 DMAc 40 10 0 0 0 0 10 40 0 0 0 0 68 DMAc 40 10 0 0 0 0 0 40 0 0 10 0 69 DMAc 40 10 0 0 0 0 0 40 0 0 0 10 70 DMAc 40 10 0 0 0 0 10 0 0 0 0 40 71 DMAc 40 10 0 0 0 0 0 0 0 0 10 40 72 DMAc 40 10 0 0 0 0 0 10 0 0 0 40 CH = cyclohexanone

The monomers were then transferred to a scintillation vial and the weigh paper used was rinsed with the solvent. The remaining volume of solvent was transferred to the vial and the vial was rendered inert with nitrogen. The sealed inert vial was then placed on a shaker overnight to produce a poly(amic acid) solution. The poly(amic acid) solution was then drop cast through a 0.45 micrometer filter onto clean glass slides, prepared in advance by cleaning with hexanes.

The coated slides were then placed on a hotplate equipped with: a thermocouple; a ramp and soak temperature controller; a nitrogen purge; and, a cover. The films were then imidized following the heating profile outlined in Table 2 and FIG. 1.

TABLE 2 Temp (° C.) time (min) 25 0 40 45 40 60 120 90 120 120 160 150 160 165 200 180 200 195 300 210

Upon completion of the imidization reaction, the films so produced were removed from the glass slide for use in later examples, or for thorough property testing.

TABLE 3 CTE Tg Solubility**** Metal Equilib Moisture Example (ppm/° C.) (° C.) DMAc NMP Adhesion moisture (%) absorption (%) 1 42 318*** 2 41* 184*** 6 41* 187 9 45* 349 1.6 4.3 11 44* 285 13 41** 204 16 43** 202*** 17 41** 223 18 44** 200*** 20 18 343 − − 1.2 4.2 24 45 314 + + 3 25 50 327 26 45 + + 27 21 − + 3 1.1 3.7 28 26 320 + + 4 0.3 1.9 29 23 − − 2 0.2 0.9 30 41* 31 41*/44 1 2.2 32 42* 33 48* 190 34 51* 35 47** 319 + + 5 1.5 3.3 36 41** 246 − − 2 0.9 4.3 37 20** − − 1 0.3 1.8 39 48** 40 47** 41 48** 42 43** 45 43 46 45* 48 43 49 40** 287 51 24** − − 2 0 1.7 52 19** ND − − 2 0.7 4.3 57 48 58 43 59 39 60 19 62 48 63 45 64 44 65 37 66 38 67 21 ND 68 20 ND *CTE Measured from 30-150° C. **CTE Measured from 30-175° C. ***Tg determined by DMA ND - no Tg detected by DSC ****A + indicates at 10 wt % solids the cured film dissolves. A − indicates that at 10 wt % solids the film did not completely dissolve.

Weight % (wt %) is defined as: [weight of component/(weight of component+weight of all other components)]×100. Because the initial curing profile was not optimum for every formulation/solvent combination, some of the films were not suitable for testing described in Table 3 and thus not represented. It should be recognized by those skilled in the art that a suitable combination of solvent and thermal processing profile may be developed to make films that can be tested.

Example 73 Detailed Film Casting Example

On an analytical balance, 0.5937 g (0.001914 mol) of 4,4′-oxydiphthalic anhydride and 0.4752 g (0.001914 mol) of 4,4′-diaminodiphenylsulfone were weighed out to be with in 0.0005 g of the desired weight. The monomers were transferred to a 20 mL scintillation vial, rinsing the weigh paper with 2.0 mL of dimethylacetamide, to ensure complete transfer of the monomers. The remaining solvent (5.47 mL of dimethylacetamide) was transferred by volumetric pipette to give a solution of 12.5 weight % solids. The vial was rendered inert by flowing nitrogen through the vial for one minute and then quickly capping the vial. The sample was then placed on the shaker overnight to form a poly(amic acid) solution.

Glass slides (Fisherbrand precleaned microscope slides) were cleaned with hexanes. The solution (2.0 mL) was then filtered through a 0.45 micrometer syringe tip filter onto a glass slide. The solution coated glass slide was then placed on a hotplate equipped with a ramp and soak temperature controller, a cover, and a controlled nitrogen purge of 85 liters (3 cubic feet) per hour (apparatus volume of 0.1 cubic feet). The sample was then imidized using the thermal profile outline described above for examples 1-8 and detailed in Tables 3 and FIG. 1. Following imidization the film was released from the glass slide by immersion in water at 25° C., to yield a freestanding polyimide film. The film was then used for later examples or submitted for testing and analysis.

Example 74 Detailed Film Casting Example

On an analytical balance, 0.8113 g of 4,4′-oxydiphthalic anhydride and 0.0566 g of meta-phenylene diamine and 0.2263 g of para-phenylene diamine were weighed out to be with in 0.0005 g of the desired weight. The monomers were transferred to a 20 mL scintillation vial, rinsing the weigh paper with 1.0 mL of dimethylacetamide, to ensure complete transfer of the monomers. The remaining solvent (5.47 mL of dimethylacetamide) was transferred by volumetric pipette to give a solution of 12.5 weight % solids. The vial was rendered inert by flowing nitrogen through the vial for one minute and then quickly capping the vial. The sample was then placed on the shaker overnight to form a poly(amic acid) solution.

Glass slides (Fisherbrand precleaned microscope slides) were cleaned with hexanes. The solution (2.0 mL) was then filtered through a 0.45 micrometer syringe tip filter onto a glass slide. After the solution was filtered onto the slide a 635 micrometer doctor blade (25 mil gap) was used to yield a wet film. (final film thickness is a function of concentration and gap on the doctor blade).

The solution coated glass slide was then placed on a hotplate equipped with a ramp and soak temperature controller, a cover, and controlled nitrogen purge of 85 liters (3 cubic feet) per hour (apparatus volume of 0.1 cubic feet). The sample was then imidized using the thermal profile outline described above for examples 1-72 and detailed in Tables 2 and FIG. 1. Following imidization the film was released from the glass slide by immersion in water at 25° C., to yield a freestanding polyimide film. The film was then used for later examples or submitted for testing and analysis.

Example 75

Additional examples were performed with the following terms being defined:

DSC: Differential Scanning Calorimetry was conducted on a Perkin Elmer DSC 7 with a heating rate of 20° C./min and the glass transition measured in the second heat. This method is based upon ASTM D3418.

DMA: Film samples cut precisely to give known length width and thickness were analyzed on a dynamic mechanical analyzer in a tensile mode with a frequency of 1 Hz and heating rate of 5° C./min over the temperature range 40-350° C. Dynamic mechanical analysis (DMA) is conducted in accordance to ASTM test D5026, with the exception that only one test specimen is tested. The glass transition temperature (Tg) is determined by the maximum point of the tan delta curve.

TMA: CTE values of the cast films were measured on a thermo-mechanical analyzer with a heating rate of 5° C./min from 0-250° C. CTE values were calculated from the slope over the range of 30-200° C.

Equilibrium water: The equilibrium water content was defined as the moisture content of films allowed to stand at ambient conditions in the lab for 72 h (about 25° C. and 70% RH). The moisture content was measured by accurately weighing a sample of film 10.2 centimeters×1.27 centimeters×63.5 micrometers (about 4 inch×0.5 inch×0.0025 inch) before and after a drying. Films were weighed (to 0.00005 g), dried in a 150° C. oven for 4 h, and then immediately weighed to determine the moisture loss. Equilibrium water content is the mass lost upon heating divided by the mass of the dried film as a percent.

Moisture absorption: Dried film samples (oven at 15° C. for 4 h) of known mass were submerged in water for 72 h at ambient temperature (25° C.). Following the time period, the films were removed from the water and the excess moisture removed by drying with a Kimwipe. Moisture absorption is the mass uptake upon soaking in water divided by the weight of the dried film as a percent.

Solubility: A positive result indicates that at a concentration of 10% solids, the fully imidized film cast from the poly(amic acid) solution dissolves in dimethylacetamide or N-methylpyrrolidinone (solvent indicated in the test) and can pass through a 0.45 micrometer filter.

Example 76, Part A Modification of Nano Clays

Procedure for the Preparation of Organically Modified Clay:

The organically modified clay was prepared via ion exchange in water or a combination of water and an alcohol, or water and acetonitrile. The Na⁺ MMT (a clay with sodium counter ions) was dispersed in water or water/solvent combination at 1-5% by weight and heated to 80° C. The organic cation, tetraphenylphosphonium bromide, was dissolved or dispersed water or solvent combination as above in a ratio such that when the solution or dispersion of the organic cation was added to the clay dispersion there is organic cations equal to or in excess of the cation ion exchange capacity of the dispersed clay. The mixture was then heated to reflux for 1-2 h. Following cooling to room temperature, the modified clay is collected by centrifugation. The supernatant was poured off, and the solid modified clay was washed by redispersing the clay in deionized water or deionized water solvent combination and recollected by centrifugation. The wash solution was poured off and the wash process is repeated twice more. Following the final centrifugation, the solid clay was dried in an oven and then ground to a fine powder.

Example 76, Part B

Detailed example: 2.0 g of Na⁺ MMT clay (cation exchange capacity of 0.000926 mols Na⁺/g of clay; 0.001852 mols of cations total) was dispersed in 200 mL of a 50/50 mixture of deionized water and ethanol and brought to reflux. Tetraphenylphosphonium bromide (1.4167 g, 0.002216 mols) was added and the dispersion was allowed to stir at reflux for two hours. The mixture was cooled to room temperature and transferred to four 50 mL centrifuge tubes. The tubes were placed on a centrifuge and spun at 3000 rpm for 5 min. The supernatant is poured off and redispersing the clay in fresh mixture of 50/50 deionized water and ethanol washes the remaining solid, and solid was again collected again by centrifugation. The wash procedure was repeated twice more. Following the final centrifugation and decantation the remaining solid was dried in a 120° C. oven for two hours and then ground to a fine powder. Table 4 shows the properties of organic modified montmorillonite.

TABLE 4 Wt loss at Wt loss on TGA TGA 5% loss 400° C. d-Spacing MW of under N₂ at under N₂ under N₂ for Modifier (Angstroms) modifier 900° C.(%) (° C.) 30 min(%) TPP

17.8 339.4 25.0 449.0 3.1

Example 77 Detailed Experimental Method of Lowering the CTE of a Film Using Aluminum(AcAc)₃

Soluble nanoparticle precursors: Aluminum(acetylacetonate)₃ was added to a solution of poly(amic acid) prepared as above in any of examples 1-72, or a solution of a soluble polyimide in DMAc to give a solution with 5-30 wt % polyimide precursor or polyimide and 0.5%-31.8% Al(acac)₃. The solution was then filtered onto a glass slide. The coated substrate was then placed on the hotplate and subjected to a thermal profile described in examples 1-72 as described above to complete imidization. The films so formed were then removed from the glass slide and used in later examples, or subjected to analysis.

Example 78 Detailed Experimental Analysis of Adhesion of Films to Copper

Metal Adhesion: 2.54 centimeter square (one inch square) film samples were sandwiched between two pieces of copper foil. One piece of foil has a roughened granular surface to enhance adhesion, the other copper surface was polished smooth. The stack was then pressed between the parallel plates of a heated press at 421° C. (790° F.) for one minute with three tons of pressure on the hydraulic ram. The adhesion of the film to copper was then graded using a scale of 1-5. A one indicates no adhesion to either surface. A two indicates moderate adhesion to the roughened copper. A three indicates good adhesion to the roughened copper surface, a four indicates good adhesion to the roughened surface and moderate adhesion to the smooth surface. A five indicates good adhesion to both copper surfaces equal to or better than the benchmark films. The benchmark materials are GE resins XH6050 extruded film and CRS5001 extruded film.

Example 79 Detailed Example of Solvent Cast Film with Nano Filler for Lowering CTE

TPP-MMT (Tetraphenylphosphonium treated montmorillonite clay) was dispersed in NMP solvent with the aid of sonication. Oxydianiline (ODA) was added to the resulting solution and mechanically stirred until the diamine was completely dissolved at room temperature. Oxydiphthalic dianhydride (ODPA) was then added to the solution and dispersed with mechanical stirring to form a viscous poly(amic acid) solution at 20 wt % solids. The solution was allowed to react at room temperature for 12 hours. The solution was cast onto a glass substrate at 70° C. and imidized by successive heating at 70° C. for 2 hours, 150° C. for 4 hours, 200° C. for 1 hour and 300° C. for 1 hour. The resulting nano filled polyimide film was peeled from the glass substrate for testing.

TABLE 5 CTE Normalized % (ppm/° C.) % CTE CTE Weight % 2nd scan Reduction Reduction Sample # Polymer Nanoclay Silicate (0-200) (2nd scan) (2nd scan) 49-42A1 44ODPA- None 0 44.0 0% 44ODA 49-074A1 44ODPA- TPPBr 3.8 39.4 11% 2.8% 44ODA 49-074A2 44ODPA- TPPBr 7.5 37.2 15% 2.1% 44ODA 49-074A3 44ODPA- TPPBr 15.0 30.9 30% 2.0% 44ODA

Example 80 Film Recycle Example

Film scrap of example 11 (40ODPA/10BPDA//40DDS/10pPD) was dissolved in 120° C. DMAc at 5 wt % solids. The solution was filtered through a 0.45 micrometer filter. The solution was then cast upon a glass substrate and heated slowly on a hotplate equipped with a ramp and soak temperature controller, a cover and a controlled nitrogen purge. The temperature was slowly raised to 200° C. over 4 h maintaining a partial atmosphere of DMAc vapor for the first three hours to control the solvent evaporation rate. The resulting polyimide film was released from the glass substrate by immersion in water and allowing the water to float the film from the substrate.

Example 81 Film Recycle Example

Alternatively the polyimide solution from example 80 was combined with monomers to give a solution of polyimide and poly(amic acid). 1.0 g of film from example 11 was dissolved in 7 g of DMAc to give a solution of 12.5 wt % solids as in example 80. A poly(amic acid) solution of example 11 was formulated and the two solutions were combined to give a final solution of 12.5 wt % solids. 1-20% of the composition resulting from redissolved scrap film would be suitable for this procedure. The solution was then cast upon a glass substrate and imidized with the thermal profile in Example 1 and released from the substrate.

Example 82 Film Recycle Example

Alternatively, the polyimide film scrap of example 11 was ground to a powder using a mill and then blended with a polyetherimide resin such as the GE resin XH6050 or other high performance polymer (such as polyetherketone or polysulfone) by first mixing the two powders in a shaker with up to 30% by weight ground film scrap. The powder/powder blend was then extruded on a single or twin screw extruder and pelletized. The blend was then either molded into a finished part by injection molding or is extruded into a film.

Example 83 Solubility Testing Examples: Applicable to any Films

A piece of film with the formulation 40ODPA/10BPDA//40DDS/10pPD by weight with a mass of 0.6420 g was added to a vial containing 10 mL of dimethylacetamide. The vessel was inerted with nitrogen and capped. The contents were heated at 120° C. for 24 h with gentle stirring. The solution after 24 h hours was yellow in color with a slight haziness and no pieces of the film remaining. The solution was then easily passed through a 0.45 micrometer filter with >90% of the solids content passing the filter to give a yellow, transparent solution.

Example 84 Solubility Testing Examples: Applicable to any Film from Examples 1-172

A piece of film with the formulation 50ODPA//50DDS with a mass of 0.05834 g was added to a vial containing 1.080 mL of N-methylpyrrolidinone. The vessel was inerted with nitrogen and capped. The contents were heated at 120° C. for 12 h. The solution after 12 h hours was dark amber in color and no pieces of the film remaining. The solution was then easily passed through a 0.45 micrometer filter with >90% of the solids content passing the filter to give a yellow, transparent solution.

Example 85 Solubility Testing Examples: Applicable to any Film from Examples 1-72

A piece of film with the formulation 50ODPA//10DDS/40pPD (example 51) with a mass of 0.3100 g was added to a vial containing 5.741 mL of dimethylacetamide. The vessel was inerted with nitrogen and capped. The contents were heated at 120° C. for 12 h. The solution after 12 h was pale yellow in color and a substantial amount of the film remained intact.

Example 86 Using Reactivity Differences to Make Block Co-Polymers: Ester-Acid Method

On an analytical balance, 0.7825 g (1.5033 mmol) of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride was weighed out to be within 0.0005 g of desired value and 0.16256 g (1.5033 mmol) of m-phenylenediamine was weighed out to be with in 0.0005 g of desired value. The monomers were transferred to a 20 mL scintillation vial. The weigh paper used is rinsed with 1.0 mL of dimethylacetamide, ensuring complete transfer of the monomers to the vial. More solvent (4.97 mL of dimethylacetamide) is transferred by volumetric pipette to give a solution of the first pair of monomers of the copolymer. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The sample was then placed on a shaker overnight to form the poly(amic acid).

On an analytical balance, 0.1166 g (0.3758 mmol) of the diacid-diethanol ester of pyromellitic dianhydride was weighed out to be within 0.0005 g of desired value and 0.04064 g (0.3758 mmol) of m-phenylenediamine was weighed out to be within 0.0005 g of desired value. The monomers were transferred into the 20 mL scintillation vial containing the amid-acid mixture prepared above. The weigh paper was rinsed with 1.49 mL of dimethylacetamide, ensuring complete transfer of the monomers to the vial. This gives a solution of about 12.5% solids polyimide. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The sample was then placed on the shaker for 1 hour to assure mixing.

Glass slides (Fisherbrand precleaned microscope slides) were cleaned with hexanes. The solution (2.0 mL) was then filtered through a 0.45 micrometer syringe tip filter onto the glass slide. The solution coated glass slide was then placed on a hotplate equipped with a ramp and soak temperature controller, a cover, and a controlled nitrogen purge of 85 liters (3 cubic feet) per hour (apparatus volume of 0.1 cubic feet). The sample was then imidized using the thermal profile in Table 6:

TABLE 6 temp (° C.) time (min) 25 0 40 45 40 60 120 90 120 120 160 150 160 165 200 180 200 195 300 210

Glass slides (Fisherbrand precleaned microscope slides) were cleaned with hexanes. The solution (2.0 mL) was then filtered through a 0.45 micrometer syringe tip filter onto the glass slide. The solution coated glass slide was then placed on a hotplate equipped with a ramp and soak temperature controller, a cover, and controlled nitrogen purge of 85 liters (3 cubic feet) per hour (apparatus volume of 0.1 cubic feet). The sample was then imidized using the thermal profile in Table 6.

Following imidization the film was released from the glass slide by immersion in water at 25° C., yielding a freestanding polyimide film. The film was then submitted for testing and analysis.

Example 87 Using Reactivity Differences to Make Blocky Polymers

On an analytical balance, 0.2657 g (0.903 mmol) of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) was weighed out to be with in 0.0005 g of desired value and 0.0977 g (0.9032 mmol) of para-phenylenediamine (pPD) was weighed out to be with in 0.0005 g of desired value. The monomers were transferred to a 20 mL scintillation vial. The weigh paper is rinsed with 1.0 mL of dimethylacetamide, ensuring complete transfer of the monomers to the vial. More solvent (2.74 mL of dimethylacetamide) was transferred by volumetric pipette to give a solution of the first pair of monomers of the copolymer. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The sample was then placed on the shaker for 3 hours to form the poly(amic acid).

On an analytical balance, 0.4701 g (0.9032 mmol) of the 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) was weighed out to be within 0.0005 g of desired value and 0.2243 g (0.9032 mmol) of 4,4′-diaminodiphenylsulfone (DDS) was weighed out to be within 0.0005 g of desired value. The monomers were transferred into the 20 mL scintillation vial containing the poly(amic acid) mixture prepared above. The weigh paper was rinsed with 1.0 mL of dimethylacetamide, ensuring complete transfer of the monomers and then 2.74 mL more of the dimethylacetamide was added to give the final reaction mixture. This gave a solution of about 12.5% solids polyimide. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The sample was then placed on the shaker for 12 hours to assure mixing.

Glass slides (Fisherbrand precleaned microscope slides) were cleaned with hexanes. The solution (2.0 mL) was then filtered through a 0.45 micrometer syringe tip filter onto the glass slide. The solution coated glass slide was then placed on a hotplate equipped with a ramp and soak temperature controller, a cover, and controlled nitrogen purge of 85 liters (3 cubic feet) per hour (apparatus volume of 0.1 cubic feet). The sample was then imidized using the thermal profile in Table 7:

TABLE 7 temp (° C.) time (min) 25 0 40 45 40 60 120 90 120 120 160 150 160 165 200 180 200 195 300 210

Following imidization the film was released from the glass slide by immersion in water at 25° C., yielding a freestanding polyimide film. The film was then submitted for testing and analysis.

Example 88 Using Kinetics and Process Parameters to Make Block Co-Polymers

Two Vessel Method.

On an analytical balance, 0.0892 g (0.3033 mmol) of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) was weighed out to be within 0.0005 g of desired value and 0.0328 g (0.3033 mmol) of m-phenylenediamine (MPD) was weighed out to be within 0.0005 g of desired value. The monomers were transferred to a 20 mL scintillation vial (Vial#1). The weigh paper was rinsed with 2.0 mL of dimethylacetamide, ensuring complete transfer of the monomers to Vial #1. More solvent (1.0 mL of dimethylacetamide) was transferred by volumetric pipette to give a solution of the first pair of monomers of the copolymer. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The sample was then placed on the shaker for 24 hours to form the poly(amic acid).

On an analytical balance, 0.6314 g (1.2130 mmol) of the 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) was weighed out to be within 0.0005 g of desired value and 0.3012 g (1.2130 mmol) of 4,4′-diaminodiphenylsulfone (DDS) was weighed out to be within 0.0005 g of desired value. The monomers were transferred into a second 20 mL scintillation vial (Vial#2). The weigh paper was rinsed with 1.0 mL of dimethylacetamide, ensuring complete transfer of the monomers. More solvent (3.47 mL of dimethylacetamide) was transferred by volumetric pipette to give a solution of the second pair of monomers of the copolymer. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The sample was then placed on the shaker for 24 hours to form the poly(amic acid).

After mixing, the contents of Vial #2 was added to Vial#1 and rinsed with 2 mL of dimethylacetamide to ensure complete transfer. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The vial was placed on the shaker for 30 minutes. This gave a solution of about 12.5% solids polyimide copolymer.

Glass slides (Fisherbrand precleaned microscope slides) were cleaned with hexanes. The solution (2.0 mL) was then filtered through a 0.45 micrometer syringe tip filter onto the glass slide. The solution coated glass slide was then placed on a hotplate equipped with a ramp and soak temperature controller, a cover, and a controlled nitrogen purge of 85 liters (3 cubic feet) per hour (apparatus volume of 0.1 cubic feet). The sample was then imidized using the thermal profile in Table 8:

TABLE 8 temp (° C.) time (min) 25 0 40 45 40 60 120 90 120 120 160 150 160 165 200 180 200 195 300 210

Example 89 Using Preformed Imide Polymers and Process to Make Block Co-Polymers. Two Vessel Method

On an analytical balance, 0.6894 g (0.9408 mmol) of Ultem®6050 (homopolymer of BPADA and DDS) was weighed out to be within 0.0005 g of desired value, the polymer was transferred to a 20 mL scintillation vial (Vial#1). The weigh paper was rinsed with 2.0 mL of dimethylacetamide, ensuring complete transfer of the monomers to the vial. More solvent (2.74 mL of dimethylacetamide) was transferred by volumetric pipette to give a solution of the polymer. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The sample was then placed on the shaker for 12 hours.

On an analytical balance, 0.2782 g (0.8967 mmol) of the 4,4′-oxydiphthalic dianhydride (ODPA) was weighed out to be within 0.0005 g of desired value and 0.0970 g (0.8967 mmol) of p-phenylenediamine (PPD) was weighed out to be within 0.0005 g of desired value. The monomers were transferred into a second 20 mL scintillation vial (Vial#2). The weigh paper was rinsed with 2.0 mL of dimethylacetamide, ensuring complete transfer of the monomers. More solvent (1.74 mL of dimethylacetamide) was transferred by volumetric pipette to give a solution of the second pair of monomers of the copolymer. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The sample was then placed on the shaker for 12 hours to form the poly(amic acid).

After mixing, the contents of Vial #2 was added to Vial#1 and rinsed with 1 mL of dimethylacetamide to ensure complete transfer to Vial #2. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The vial was placed on the shaker for 6 hours. This gave a solution of about 12.5% solids polyimide copolymer.

Glass slides (Fisherbrand precleaned microscope slides) were cleaned with hexanes. The solution (2.0 mL) was then filtered through a 0.45 micrometer syringe tip filter onto the glass slide. The solution coated glass slide was then placed on a hotplate equipped with a ramp and soak temperature controller, a cover, and controlled nitrogen purge of 3 cubic feet per hour (apparatus volume of 0.1 cubic feet). The sample was then imidized using the thermal profile in Table 9:

TABLE 9 temp (° C.) time (min) 25 0 40 45 40 60 120 90 120 120 160 150 160 165 200 180 200 195 300 210

Following imidization the film was released from the glass slide by immersion in water at 25° C., yielding a freestanding polyimide film. The film was then submitted for testing and analysis.

Example 90 Using Preformed Imide Prepolymer or Polymer and Process to Make Random Co-Polymers, Ambient Temperature Method

On an analytical balance, 0.9255 g (1.2630 mmol) of Ultem®6050 (homopolymer of BPADA and DDS) was weighed out to be within 0.0005 g of desired value and 0.0326 g (0.3018 mmol) of m-phenylenediamine (MPD) was weighed out to be within 0.0005 g of desired value. The polymer and diamine were transferred to a 20 mL scintillation vial (Vial#1). The weigh paper was rinsed with 2.0 mL of dimethylacetamide, ensuring complete transfer of the monomers. Water (0.01 mL) and more solvent (4.98 mL of dimethylacetamide) was transferred by volumetric pipette to give a solution of the polymer and diamine and water. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The sample was then placed on the shaker for 24 hours. (The mixture can optionally be heated at this point to about 50° C. while shaking to aid the randomization reaction).

After the 24 hours, 0.0936 g (0.3018 mmol) of the 4,4′-oxydiphthalic dianhydride (ODPA) was weighed out to be within 0.0005 g of desired value. The dianhydride was transferred into the 20 mL scintillation vial (Vial#1). The weigh paper was rinsed with 1.49 mL of dimethylacetamide, ensuring complete transfer of the monomer. The vial was inerted with nitrogen by flowing nitrogen through the vial for one minute and quickly capping the vial. The sample was then placed on the shaker for 12 hours to form the random poly(amic acid). This gave a solution of about 12.5% solids polyimide copolymer.

Glass slides (Fisherbrand precleaned microscope slides) were cleaned with hexanes. The solution (2.0 mL) was then filtered through a 0.45 micrometer syringe tip filter onto the glass slide. The solution coated glass slide was then placed on a hotplate equipped with a ramp and soak temperature controller, a cover, and controlled nitrogen purge of 85 liters (3 cubic feet) per hour (apparatus volume of 0.1 cubic feet). The sample was then imidized using the thermal profile:

TABLE 10 temp ° C. time (min) 25 0 40 45 40 60 120 90 120 120 160 150 160 165 200 180 200 195 300 210

Following imidization the film was released from the glass slide by immersion in water at 25° C., yielding a freestanding polyimide film. The film was then submitted for testing and analysis.

Examples 91-204

Examples 91-204 listed in Table 11 were prepared according to the method described for examples 1-72

Casting Procedure: The correct mol ratios of dianhydride and diamine as shown in Table 11 were weighed on an analytical balance to four decimal place accuracy.

TABLE 11 Dianhydrides Diamines ODPA BPDA BTDA BPhDA PMDA BPADA DDS PPD 133 APB 134 APB MPD ODA Ex. Solvent (%) (%) (%) (%) (%) (%) (%) (%) (%) %) (%) (%) 91 NMP/CH 40 10 0 0 0 0 50 0 0 0 0 0 92 NMP/CH 40 10 0 0 0 0 40 10 0 0 0 0 93 NMP/CH 40 10 0 0 0 0 10 40 0 0 0 0 94 DMAc 50 0 0 0 0 0 50 0 0 0 0 0 95 DMAc 50 0 0 0 0 0 0 0 50 0 0 0 96 DMAc 50 0 0 0 0 0 0 50 0 0 0 0 97 DMAc 50 0 0 0 0 0 0 0 0 0 50 0 98 DMAc 40 10 0 0 0 0 0 0 50 0 0 0 99 DMAc 45 5 0 0 0 0 0 50 0 0 0 0 100 DMAc 45 0 5 0 0 0 0 50 0 0 0 0 101 DMAc 5 0 45 0 0 0 0 50 0 0 0 0 102 DMAc 45 0 5 0 0 0 50 0 0 0 0 0 103 DMAc 5 0 45 0 0 0 50 0 0 0 0 0 104 DMAc 45 5 0 0 0 0 0 15 35 0 0 0 105 DMAc 45 0 5 0 0 0 0 15 35 0 0 0 106 DMAc 5 0 45 0 0 0 0 15 35 0 0 0 107 DMAc 50 0 0 0 0 0 0 15 35 0 0 0 108 DMAc 40 10 0 0 0 0 50 0 0 0 0 0 109 DMAc 40 10 0 0 0 0 0 50 0 0 0 0 110 DMAc 40 10 0 0 0 0 40 10 0 0 0 0 111 DMAc 40 10 0 0 0 0 10 40 0 0 0 0 112 NMP 45 0 0 5 0 0 50 0 0 0 0 0 113 NMP 0 0 45 5 0 0 50 0 0 0 0 0 114 NMP 45 0 0 5 0 0 0 15 35 0 0 0 115 NMP 0 0 45 5 0 0 0 15 35 0 0 0 116 DMAc 45 0 0 5 0 0 0 0 50 0 0 0 117 DMAc 45 0 0 5 0 0 50 0 0 0 0 0 118 DMAc 45 0 0 5 0 0 0 15 35 0 0 0 119 DMAc 0 5 0 0 0 45 0 15 35 0 0 0 120 DMAc 0 0 0 0 0 50 0 15 35 0 0 0 121 DMAc 50 0 0 0 0 0 50 0 0 0 0 0 122 DMAc 50 0 0 0 0 0 0 0 0 0 50 0 123 DMAc 50 0 0 0 0 0 0 50 0 0 0 0 124 DMAc 50 0 0 0 0 0 40 0 0 0 10 0 125 DMAc 50 0 0 0 0 0 40 10 0 0 0 0 126 DMAc 50 0 0 0 0 0 40 0 0 0 0 10 127 DMAc 50 0 0 0 0 0 10 0 0 0 40 0 128 DMAc 50 0 0 0 0 0 0 10 0 0 40 0 129 DMAc 50 0 0 0 0 0 10 40 0 0 0 0 130 DMAc 50 0 0 0 0 0 0 40 0 0 10 0 131 DMAc 50 0 0 0 0 0 0 40 0 0 0 10 132 DMAc 50 0 0 0 0 0 10 0 0 0 0 40 133 DMAc 40 10 0 0 0 0 50 0 0 0 0 0 134 DMAc 40 10 0 0 0 0 0 0 0 0 50 0 135 DMAc 40 10 0 0 0 0 0 50 0 0 0 0 136 DMAc 40 10 0 0 0 0 40 0 0 0 10 0 137 DMAc 40 10 0 0 0 0 40 10 0 0 0 0 138 DMAc 40 10 0 0 0 0 40 0 0 0 0 10 139 DMAc 50 0 0 0 0 0 10 0 0 0 40 0 140 DMAc 50 0 0 0 0 0 0 0 0 50 0 0 141 DMAc 50 0 0 0 0 0 40 0 0 10 0 0 142 DMAc 50 0 0 0 0 0 0 0 0 10 40 0 143 DMAc 50 0 0 0 0 0 0 40 0 10 0 0 144 DMAc 50 0 0 0 0 0 10 0 0 40 0 0 145 DMAc 50 0 0 0 0 0 0 0 0 40 10 0 146 DMAc 50 0 0 0 0 0 0 10 0 40 0 0 147 DMAc 50 0 0 0 0 0 0 0 0 40 0 10 148 DMAc 40 10 0 0 0 0 0 0 0 50 0 0 149 DMAc 40 10 0 0 0 0 40 0 0 10 0 0 150 DMAc 40 10 0 0 0 0 0 0 0 0 40 10 151 DMAc 40 10 0 0 0 0 0 40 0 10 0 0 152 DMAc 40 10 0 0 0 0 10 0 0 40 0 0 153 DMAc 40 10 0 0 0 0 0 0 0 40 10 0 154 DMAc 40 10 0 0 0 0 10 0 0 40 0 0 155 DMAc 40 10 0 0 0 0 0 10 0 0 40 0 156 DMAc 40 10 0 0 0 0 0 0 0 0 40 10 157 DMAc 40 10 0 0 0 0 10 40 0 0 0 0 158 DMAc 40 10 0 0 0 0 0 40 0 0 10 0 159 DMAc 50 0 0 0 0 0 5 45 0 0 0 0 160 DMAc 50 0 0 0 0 0 0 45 0 0 5 0 161 DMAc 50 0 0 0 0 0 0 35 0 0 15 0 162 DMAc 45 5 0 0 0 0 50 0 0 0 0 0 163 DMAc 45 5 0 0 0 0 10 40 0 0 0 0 164 DMAc 45 5 0 0 0 0 0 0 0 0 40 10 165 DMAc 45 5 0 0 0 0 0 40 0 0 10 0 166 DMAc 40 0 10 0 0 0 50 0 0 0 0 0 167 DMAc 40 10 0 0 0 0 35 15 0 0 0 0 168 DMAc 40 10 0 0 0 0 45 5 0 0 0 0 169 DMAc 40 10 0 0 0 0 5 45 0 0 0 0 170 DMAc 40 10 0 0 0 0 15 35 0 0 0 0 171 DMAc 40 10 0 0 0 0 0 0 0 0 45 5 172 DMAc 0 0 0 0 0 50 50 0 0 0 0 0 173 DMAc 0 0 0 0 0 50 0 0 0 0 50 0 174 DMAc 0 0 0 0 0 50 0 50 0 0 0 0 175 DMAc 0 0 50 0 0 0 0 0 0 0 50 0 176 DMAc 0 0 50 0 0 0 0 0 0 0 0 50 177 DMAc 0 0 50 0 0 0 0 0 0 0 50 0 178 DMAc 50 0 0 0 0 0 45 5 0 0 0 0 179 DMAc 50 0 0 0 0 0 25 25 0 0 0 0 180 DMAc 45 5 0 0 0 0 30 20 0 0 0 0 181 DMAc 45 5 0 0 0 0 30 20 0 0 0 0 182 DMAc 45 5 0 0 0 0 0 30 0 0 20 0 183 DMAc/NMP 40 10 0 0 0 0 40 10 0 0 0 0 184 DMAc/NMP 45 5 0 0 0 0 0 50 0 0 0 0 185 DMAc/NMP 50 0 0 0 0 0 0 40 0 0 10 0 186 DMAc/NMP 40 10 0 0 0 0 0 10 0 0 40 0 187 DMAc/NMP 40 10 0 0 0 0 50 0 0 0 0 0 188 DMAc/NMP 50 0 0 0 0 0 0 0 0 0 50 0 189 DMAc/NMP 50 0 0 0 0 0 50 0 0 0 0 0 190 DMAc/NMP 40 10 0 0 0 0 0 0 0 0 40 10 191 DMAc 50 0 0 0 0 0 0 20 0 0 30 0 192 DMAc 50 0 0 0 0 0 0 30 0 0 20 0 193 DMAc 15 0 0 0 0 35 0 50 0 0 0 0 194 DMAc 50 0 0 0 0 0 0 50 0 0 0 0 195 DMAc 25 0 0 0 0 25 0 50 0 0 0 0 196 DMAc 15 0 0 0 0 35 0 50 0 0 0 0 197 DMAc 5 0 0 0 0 45 0 50 0 0 0 0 198 DMAc 40 0 10 0 0 0 0 50 0 0 0 0 199 DMAc 45 0 0 0 0 5 0 15 0 0 35 0 200 DMAc 45 0 0 0 0 5 0 35 0 0 15 0 201 DMAc 40 0 0 0 0 10 0 25 0 0 25 0 202 DMAc 35 0 0 0 0 15 0 15 0 0 35 0 203 DMAc 35 0 0 0 0 15 0 35 0 0 15 0 204 DMAc 45 0 0 0 0 5 0 15 0 0 35 0

The monomers were then transferred to a scintillation vial and the weigh paper used was rinsed with the solvent. The remaining volume of solvent was transferred to the vial and the vial was rendered inert with nitrogen. The sealed inert vial was then placed on a shaker overnight to produce a poly(amic acid) solution. The poly(amic acid) solution is then drop cast through a 0.45 micrometer filter onto clean glass slides, prepared in advance by cleaning with hexanes.

The coated slides were then placed on a hotplate equipped with: a thermocouple; a ramp and soak temperature controller; a nitrogen purge; and, a cover. The films were then imidized following the heating profile outlined in FIG. 1 and Table 2.

Upon completion of the imidization reaction, the films so produced were removed from the glass slide for use in later examples, or for thorough property testing. The physical property measurements for Examples 91-204 are listed in Table 12.

TABLE 12 Tg (DSC) CTE Tg (DMA) Metal Equilib moisture Moisture Ex (° C.) (ppm/° C.) (° C.) Adhesion (%) absorption (%) 91 349 45 305 5 1.6 4.3 92 286 44 305 93 241 94 302 42 318 95 186 41 184 96 343 97 ND 98 187 41 187 99 343 18 337 3 1.2 4.2 100 ND 101 ND 102 314 45 323 103 327 50 334 104 204 41 200 105 207 43 202 106 223 41 220 107 202 44 200 108 318 45 320 109 ND 21 315 3 1.1 3.7 110 313 26 320 4 0.3 1.9 111 ND 23 300 2 0.2 0.9 112 343 113 312 42 326 114 197 45 201 115 41 230 116 188 43 190 117 293 41/44 307 3 1 2.2 118 203 43 203 119 190 50 188 120 188 52 188 121 319 47 324 5 1.5 3.3 122 246 41 2 0.9 4.3 123 20 331 1 0.3 1.8 124 298 48 125 301 47 311 126 278 48 127 294 43 128 287 40 285 129 ND 24 324 2 0 1.7 130 ND 19 309 4 0.7 4.3 131 289 132 343 133 46 328 134 41 293 135 17 136 44 320 137 45 334 138 48 301 139 41 298 140 223 48 218 141 278 43 294 142 261 40 261 143 ND 19 285 144 214 48 217 145 233 45 230 146 233 44 228 147 222 49 216 148 225 48 217 149 291 46 304 150 279 40 271 151 ND 24 275 152 244 50 239 153 233 47 233 154 244 51 238 155 302 37 296 156 271 38 267 157 ND 21 318 158 ND 20 159 298 19 160 297 19 161 205, 229 31 162 213 51 163 243, 295 46 164 269 47 165 284 27 166 ND 45 167 302 41 168 319 44 169 314 22 170 30 171 265 43 172 248 52 173 211 44 174 220 55 175 318 44 176 28 177 283 40 178 47 179 44 180 42 181 36 182 32 183 ND 184 nd 185 296 186 297 187 298 188 288 189 294 190 300 191 54 192 28 193 50 194 12 195 47 196 51 197 52 198  9 199 42 200 31 201 40 202 45 203 42 204 41 ND = no T_(g) detected

Example 205 FPC Example

On an analytical balance, 11.3387 g of 4,4′-oxydiphthalic anhydride, 1.8151 g of diaminodiphenylsulfone and 3.1620 g of para-phenylene diamine were weighed out to be with in 0.0005 g of the desired weight. The monomers were transferred to a 100 mL vial, rinsing the weigh paper with 2.0 mL of dimethylacetamide, to ensure complete transfer of the monomers. The remaining solvent (55.63 mL of dimethylacetamide) was transferred by volumetric pipette to give a solution of 12.5 weight % solids. The vial was rendered inert by flowing nitrogen through the vial for one minute and then quickly capping the vial. The sample was then placed on the shaker overnight to form a poly(amic acid) solution.

Using a syringe and a 0.45 micrometer filter, 5 mL of solution was then transferred onto a piece of smooth metallic copper foil 10.2 centimeters×20.4 centimeters, 50.8 micrometers thick (4 inches×8 inches, and 2 mil thick) pre-cleaned with isopropanol and drawn into a thin uniform coating using a 381 micrometer (15 mil) wet film applicator. The sample was then imidized using the thermal profile outline described above for examples 1-72 and detailed in Tables 2 and FIG. 1 giving a polyimide/copper laminate.

The laminate was then masked with scotch tape to give a pattern of exposed copper lines of varying width (from 1 mm to 5 mm). The exposed copper was then etched with concentrated nitric acid for one minute followed by washing with deionized water yielding a patterned laminate with discrete copper conductors.

Example 206 Wire Wrap Example #1

A film was prepared from the composition 45% 4,4′-oxydiphthalic anhydride, 5% 3,3′,4,4′-biphenyltetracarboxylic dianhydride and 50% diaminodiphenylsulfone prepared as above. The film was cut into strips 1 mm wide and 5 cm in length. The strip of film was affixed to a 16 gauge stainless steel wire at a 45 degree angle relative to the wire with a piece of tape. The strip was then tightly wrapped with 0.1 mm overlap at the edge to provide a high heat, flexible, insulating coating around the wire.

Example 207 Wire Wrap Example #2

A film was prepared from the composition 50% 4,4′-oxydiphthalic anhydride, and 10% meta-phenylene diamine and 40% para-phenylenediamine was prepared as above. The film was cut into strips 1 mm wide and 5 cm in length. The strip of film was affixed to a 18 gauge copper wire at a 45 degree angle relative to the wire with a piece of tape. The strip was then tightly wrapped with 0.1 mm overlap at the edge to provide a high heat, flexible, insulating coating around the wire.

Example 208 Capacitor

A 7.62 centimeter×7.62 centimeter (3″×3″) piece of film prepared from the composition 50% 4,4′-oxydiphthalic anhydride, and 10% meta-phenylene diamine and 40% para-phenylenediamine, as above using a 381 micrometer (15 mil) doctor blade) was placed between to pieces of 5.08 centimeters×5.08 centimeters (2 inch×2 inch) copper foil. The stack was then pressed between the parallel plates of a heated press at 404° C. (760° F.) for one minute with three tons of pressure on the hydraulic ram. The resultant article, which has an adhesion ranking of 4 by the test described previously, is a capacitor consisting of two parallel conductors separated by thin polyimide insulator.

All patents, patent applications, and other publications disclosed herein are incorporated by reference in their entirety as though set forth in full.

While the invention has been described with reference to preferred embodiment, it will be understood by those skilled in the art that various changes may be made, and equivalents substituted, for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed as the best mode contemplated for carrying out the present invention, but that the invention will include all embodiments falling within the scope of the appended claims. 

We claim:
 1. An article comprising a solvent cast film, the film comprising a thermoplastic polyimide consisting essentially of structural units derived from polymerization of a dianhydride component comprising at least 80 mole % of a dianhydride selected from the group consisting of 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4′-oxydiphthalic anhydride, and combinations thereof, based on the total moles of dianhydride with a diamine component consisting of at least 80 mole % p-phenylenediamine based on the total moles of the diamine component and up to 20 mole % of a diamine selected from the group consisting of 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, and combinations thereof; wherein the dianhydride component and the diamine component are in a molar ratio of from 1 to 1.3 moles diamine per mole of dianhydride; wherein the polyimide has a glass transition temperature of 190° C. or greater; wherein the film has a coefficient of thermal expansion of less than 30 ppm/° C. measured over 30° C. to 200° C., a thickness from 0.1 to 250 micrometers, and less than 5% residual solvent by weight; wherein the polyimide has less than 15 molar % of structural units derived from a member of the group consisting of biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, an ester of biphenyltetracarboxylic acid, and a combination thereof; and wherein the film further comprises an exfoliated nanoclay and has a lower CTE (measured over 30° C. to 200° C.) than a film of the same composition without the exfoliated nanoclay.
 2. The article of claim 1, wherein the glass transition temperature of the polyimide is from 190° C. to 500° C.
 3. The article of claim 1, wherein the dianhydride component further comprises a dianhydride selected from the group consisting of: 2,2′-bis(1,3-trifluoromethyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride; 2,2′-bis(1-methyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride; 2,2′-bis(1-phenyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride; 2,2′-bis(1-trifluoromethyl-2-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride; 2,2′-bis(1-trifluoromethyl-3-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride; 2,2′-bis(1-trifluoromethyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride; 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 2,2-bis((4-(3,3-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride; 2,2-bis((4-(3,3-dicarboxyphenoxy)phenyl)propane dianhydride; 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 2,2′-dibromo-3,3′,4,4′-biphenyltetracarboxylic dianhydride; 2,3,6,7-naphthalic dianhydride; 3,3′,4,4′-benzophenonetetracarboxylic dianhydride; 3,3′,4,4′-biphenylethertetracarboxylic dianhydride; 3,3′,4,4′-biphenylsulphonictetracarboxylic dianhydride; 3,3′,4,4′-biphenyltetracarboxylic dianhydride; 3,3′,4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride; 3,3′,4,4′-diphenylmethane tetracarboxylic dianhydride; 3,3′,4,4′-diphenylsulfide tetracarboxylic dianhydride; 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride; 3,3′,4,4′-diphenylsulfoxide tetracarboxylic dianhydride; 3,3′-benzophenone tetracarboxylic dianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; 4,4′-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; 4,4′-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride; 4,4′-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride; 4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride; 4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulphone dianhydride; 4,4′-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4′-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride; 4,4′-bisphenol A dianhydride; 4,4′-carbonyldiphthalic anhydride; 6,6′-bis(3,4-dicarboxyphenoxy)-2,2′,3,3′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indene]dianhydride; 7,7′-bis(3,4-dicarboxyphenoxy)-3,3′,4,4′-tetrahydro-4,4,4′,4′-tetramethyl-2,2′-spirobi[2H-1-benzopyran]dianhydride; bis(phthalic)phenylsulphineoxide dianhydride; bis(triphenylphthalic)-4,4′-diphenylether dianhydride; bis(triphenylphthalic)-4,4′-diphenylmethane dianhydride; hydroquinone diphthalic anhydride; m-phenylene-bis(triphenylphthalic)dianhydride; p-phenylene-bis(triphenylphthalic)dianhydride; pyromellitic dianhydride; (3,3′,4,4′-diphenyl)phenylphosphine tetracarboxylic dianhydride; (3,3′,4,4′-diphenyl)phenylphosphineoxide tetracarboxylic dianhydride; 1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride; 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride; 1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride; 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride; and a combination thereof.
 4. The article of claim 1, wherein the film comprises a combination of diamines sufficient to impart a CTE (measured over 30° C. to 200° C.) to the film that remains constant while the combination of diamines also imparts a Tg to the film from 220° C. to 375° C.
 5. The article of claim 1, wherein the solvent is selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrolidinone, dimethylsulfoxide, sulfolane, tetrahydrofuran, benzophenone, cyclohexanone, phenol, o-cresol, p-cresol, m-cresol, ethylphenol, isopropylphenol, t-butylphenol, xylenol, mesitol, chlorophenol, dichlorophenol, phenylphenol, a monoalkyl ether of ethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoalkyl ether of diethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoaryl ether glycol, a monoaryl ether of propylene glycol, tetramethylurea, phenoxy ethanol, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, N-cyclohexylpyrrolidinone, ethyl lactate, an ionic liquid, and a combination thereof.
 6. The article of claim 5, wherein the film has a Tg that is the same as a film of the same composition without the nanoclay.
 7. The article of claim 5, wherein the film is transparent.
 8. The article of claim 1, wherein the film has a coefficient of thermal expansion of at least 5 ppm/° C. measured over 30° C. to 200° C.
 9. The article of claim 1, wherein the film has a coefficient of thermal expansion of 5 ppm/° C. to 30 ppm/° C. measured over 30° C. to 200° C.
 10. The article of claim 1, wherein the film has a coefficient of thermal expansion of 10 ppm/° C. to 30 ppm/° C. measured over 30° C. to 200° C.
 11. The article of claim 1, wherein the film has a coefficient of thermal expansion of 10 ppm/° C. to 20 ppm/° C. measured over 30° C. to 200° C.
 12. The article of claim 1, wherein the film has a coefficient of thermal expansion that is within ±20 ppm/° C. (measured over 30° C. to 200° C.) of the coefficient of thermal expansion of copper, silicon, aluminum, gold, silver, nickel, a glass, a ceramic, or a polymer.
 13. The article of claim 1, wherein the film has a coefficient of thermal expansion that is within ±15 ppm/° C. (measured over 30° C. to 200° C.) of the coefficient of thermal expansion of copper.
 14. The article of claim 1, wherein the film loses less than 5% of its initial weight after storage in water for 24 hours at 25° C.
 15. The article of claim 1, wherein the film loses less than 2% of its initial weight after storage in water for 24 hours at 25° C.
 16. The article of claim 1, wherein a 10 wt % solution of the dried film in dimethylacetamide or N-methylpyrolidinone has an inherent viscosity of greater than 0.05 dl/g.
 17. The article of claim 1, wherein the film after lamination to a substrate at a temperature from 250 to 450° C. has a coefficient of thermal expansion within ±10 ppm/° C. (measured over 30° C. to 200° C.) of the coefficient of thermal expansion of the film prior to lamination.
 18. The article of claim 1, wherein the film further comprises a recycled polyimide.
 19. The article of claim 18, wherein the film comprises up to 50 wt % of a recycled polyimide, wherein prior to recycling the recycled polyimide has a glass transition temperature from 210° C. to 450° C.
 20. The article of claim 18, wherein the film comprises up to 30 wt % of a recycled polyimide film, wherein prior to recycling the recycled polyimide film has a glass transition temperature from 210° C. to 450° C.
 21. The article of claim 18, wherein the coefficient of thermal expansion of the film comprising the recycled polyimide is within ±10 ppm/° C. (measured over 30° C. to 200° C.) of the coefficient of thermal expansion of a film having the same composition without the recycled polyimide.
 22. The article of claim 18, wherein the film comprising the recycled polyimide is capable of being melt blended.
 23. The article of claim 1, wherein the film is cast from a composition comprising 1 to 30 wt % solids.
 24. The article of claim 1, wherein the polyimide film is disposed on a substrate.
 25. The article of claim 24, wherein the substrate is selected from the group consisting of copper, silicon, aluminum, gold, silver, nickel, a glass, a ceramic, and a polymer.
 26. The article of claim 24, further comprising a second substrate disposed on a side of the film opposite the first substrate.
 27. The article of claim 26, wherein the second substrate is selected from the group consisting of copper, silicon, aluminum, gold, silver, nickel, glass, ceramic, a polymer, and a combination thereof.
 28. The article of claim 1, wherein the article is a laminate further comprising a conductive layer comprising a metal, wherein the film is adheringly disposed on a face of the conductive layer.
 29. The article of claim 28, wherein the metal is copper, silver, gold, aluminum, or an alloy comprising at least one of the foregoing metals.
 30. The article of claim 1, wherein the article is a flexible printed circuit comprising a copper layer adheringly disposed on the polyimide film.
 31. The article of claim 30, wherein the flexible printed circuit further comprises a dielectric layer comprising a second material other than the polyimide of the film.
 32. The article of claim 1, wherein the article is a capacitor comprising the polyimide film disposed between a first metal substrate and a second metal substrate.
 33. The article of claim 1, further comprising an electrically conductive wire substrate, wherein the polyimide film surroundingly coats at least a portion of a surface of the wire.
 34. A method of manufacture of the article of claim 1, comprising forming the solvent cast polyimide film on a substrate.
 35. An article comprising a solvent cast polyetherimide film, the film comprising: a thermoplastic polyetherimide consisting essentially of structural units derived from the polymerization of a dianhydride component comprising at least 80 mole % of a dianhydride selected from the group consisting of 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4′-oxydiphthalic anhydride, and combinations thereof, based on the total moles of dianhydride, with a diamine component consisting of at least 80 mole % p-phenylenediamine based on the total moles of diamine and up to 20 mole % of a diamine selected from the group consisting of 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, and combinations thereof; wherein the polyetherimide comprises less than 15 mole % of structural units selected derived from the group consisting of biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, an ester of biphenyltetracarboxylic acid, and combinations thereof; wherein the dianhydride component and the diamine component are in a molar ratio of from 1 to 1.3 moles diamine per mole of dianhydride; wherein the polyetherimide has a glass transition temperature from 190° C. to 400° C., and wherein the film has a coefficient of thermal expansion of less than 30 ppm/° C. measured over 30° C. to 200° C., a thickness from 0.1 to 250 micrometers, and less than 5% residual solvent by weight; wherein the film has a coefficient of thermal expansion that is within ±20 ppm/° C. (measured over 30° C. to 200° C.) of the coefficient of thermal expansion of copper, silicon, aluminum, gold, silver, nickel, a glass, a ceramic, or a polymer; wherein the film further comprises an exfoliated nanoclay and has a lower CTE (measured over 30° C. to 200° C.) than a film of the same composition without the exfoliated nano clay; and wherein the solvent is selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrolidinone, dimethylsulfoxide, sulfolane, tetrahydrofuran, benzophenone, cyclohexanone, phenol, o-cresol, p-cresol, m-cresol, phenol, ethylphenol, isopropylphenol, t-butylphenol, xylenol, mesitol, chlorophenol, dichlorophenol, phenylphenol, a monoalkyl ether of ethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoalkyl ether of diethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoaryl ether glycol, a monoaryl ether of propylene glycol, tetramethylurea, phenoxy ethanol, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, N-cyclohexylpyrrolidinone, ethyl lactate, an ionic liquid, and combinations thereof. 